α-substituted benzyl heterocyclic derivatives, intermediates for producing the same and agrochemical composition containing the same as active ingredient

ABSTRACT

A compound represented by the formula (I): wherein R 1  is an optionally substituted heterocyclic group; R 2  is optionally substituted aryl or heterocyclic group; R 3  is hydrogen, alkyl, alkenyl, or alkynyl; R 4  is hydrogen, alkyl, alkoxy, halogen, nitro, cyano, or halogenated alkyl; M is oxygen, S(O) i  wherein i is 0, 1, or 2, NR 5  wherein R 5  is hydrogen, alkyl, or acyl, --Q--N═C(R 6 )--, --B--C(R 8 )═N--, --CH═N--N═C(R 9 )--, or --CH═N--A--(CR 10  R 11 )m--; and n is 0, 1, or 2, an intermediate for producing the same and an agrochemical composition containing the same as an active ingredient.

This is a divisional of Ser. No. 09/011,980, filed Feb. 20, 1998, nowU.S. Pat. No. 5,965,740 which is a 371 of PCT/JP96/02765, filed Sep. 25,1996.

TECHNICAL FIELD

This invention relates to a novel α-substituted benzyl heterocyclicderivative, an intermediate for producing the same, and an agrochemicalcomposition containing the same as an active ingredient.

BACKGROUND ART

Some α-substituted benzyl heterocyclic derivatives are known to havebiological activity such as herbicidal activity, fungicidal activityetc. and pharmacological activity such as anti-arrhythmic activity,sedative activity etc.

For example, JP-A 6-49039, JP-A 7-48359, and WO 94/08975 discloseα-substituted benzyl heterocyclic derivatives showing herbicidal andfungicidal activity. However, heterocyclic rings of those are limited topyrimidine and its fused rings. Further, any specific compounds havingsubstituents similar to those of this invention at the ortho position ofbenzyl are not disclosed therein.

The object of this invention is to provide compounds having more potentfungicidal and insecticidal activity.

DISCLOSURE OF INVENTION

The present inventors have intensively researched to achieve the aboveobject. As a result, it has been found that α-substituted benzylheterocyclic derivatives described below show potent fungicidal andinsecticidal activity. Thus, the present invention has beenaccomplished.

This invention relates to a compound represented by the formula (I):##STR1## wherein R¹ is an optionally substituted heterocyclic groupexcept pyrimidinyl; R² is optionally substituted aryl, or an optionallysubstituted heterocyclic group; R³ is hydrogen alkyl, alkenyl, oralkynyl; R⁴ is hydrogen, alkyl, alkoxy, halogen, nitro, cyano, orhalogenated alkyl; M is (1) oxygen, (2) S(O)_(i) wherein i is 0, 1, or2, (3) NR⁵ wherein R⁵ is hydrogen, alkyl, or acyl, (4) --Q--N═C(R⁶)--wherein Q is oxygen or NR⁷ wherein R⁷ is hydrogen, alkyl, or acyl; R⁶ ishydrogen, alkyl, acyl, alkylthio, alkylsulfinyl, alkylsulfonyl,halogenated alkyl, cyano, alkoxycarbonyl, alkoxyalkyl, optionallysubstituted amino, or cycloalkyl, or R² and R⁶ taken together form amonocyclic group or a fused polycyclic group optionally having a heteroatom, (5) --B--C(R⁸)═N-- wherein B is oxygen or sulfur and R⁸ ishydrogen, alkyl, acyl, alkylthio, alkylsulfinyl, alkylsulfonyl,halogenated alkyl, cyano, alkoxycarbonyl, alkoxyalkyl, optionallysubstituted amino, or cycloalkyl, (6) --CH═N--N═C(R⁹)-- wherein R⁹ ishydrogen, alkyl, cyano, cycloalkyl, or halogenated alkyl, or (7)--CH═N--A--(CR¹⁰ R¹¹)m-- wherein R¹⁰ and R¹¹ are independently hydrogen,alkyl, cyano, or halogenated alkyl, A is oxygen or NR¹² wherein R¹² ishydrogen, alkyl, or acyl, and m is 0 or 1; and n is 0, 1, or 2.

In this specification the term "lower" means to have 1 to 8 carbonatoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbonatoms, unless otherwise defined.

The optionally substituted heterocyclic group represented by R¹ includesan unsubstituted heterocyclic group and a substituted heterocyclicgroup. Examples of these heterocyclic groups are 5 to 7 memberedheterocyclic groups having 1 to 4 hetero atoms selected from nitrogen,sulfur, and oxygen in the ring, specifically, pyridyl such aspyridin-2-yl and pyridin-3-yl, isoxazolyl such as isoxazol-3-yl,isoxazol-4-yl, and isoxazol-5-yl, isoxazolinyl such as 2-isoxazolin-3-yland 2-isoxazolin-5-yl, isothiazolyl such as isothiazol-5-yl,thiadiazolyl such as 1,3,4-thiadiazolyl (ex. 1,3,4-thiadiazol-2-yl) and1,2,3-thiadiazolyl, pyridazinyl such as pyridazin-2-yl, pyrazolyl suchas pyrazol-1-yl and pyrazol-5-yl, furyl such as furan-2-yl, thienyl suchas thiophen-2-yl, imidazolyl such as imidazol-2-yl, oxazolyl such asoxazol-2-yl and oxazol-5-yl, thiazolyl such as thiazol-2-yl,thiazolidinyl such as thiazolidin-2-yl, oxadiazolyl such as1,3,4-oxadiazolyl (ex. 1,3,4-oxadiazol-2-yl) and 1,2,4-oxadiazolyl,triazolyl such as 1,2,4-triazolyl (ex. 1H-1,2,4-triazol-1-yl,4H-1,2,4-triazol-4-yl, and 1H-1,2,4-triazol-5-yl), pyrazinyl and thelike.

Any of these heterocyclic groups may form a fused ring with acarbocyclic ring or another heterocyclic ring. Examples of the fusedring are benzoxazolyl such as benzoxazol-2-yl, benzothiazolyl such asbenzothiazol-2-yl, benzoisoxazolyl such as benzoisoxazol-3-yl,tetramethyleneisoxazolyl such as 3,4-tetramethyleneisoxazol-5-yl and4,5-tetramethyleneisoxazol-3-yl and the like.

These heterocyclic groups and fused rings thereof may have a bond at anypossible position on the ring.

The substituents of the substituted heterocyclic group represented by R¹include, for example, lower alkyl such as methyl, ethyl, propyl, andbutyl, lower alkenyl such as vinyl, allyl, and 2-butenyl, lower alkynylsuch as ethynyl, 2-propynyl, and 3-butynyl, cycloalkyl such ascyclopropyl, cyclopentyl, and cyclohexyl, cycloalkenyl such ascyclopentenyl and cyclohexenyl, lower alkanoyl such as acetyl,propionyl, and isobutyryl, lower alkylsilyl such as methylsilyl,ethylsilyl, propylsilyl, and butylsilyl, halogenated lower alkyl such astrifluoromethyl, trichloromethyl, chloromethyl, 2-bromoethyl, and1,2-dichloropropyl, di(lower)alkylamino such as dimethylamino anddiethylamino, phenyl, phenyl(lower)alkyl such as benzyl and phenethyl,phenyl(lower)alkenyl such as styryl and cinnamyl, furyl(lower)alkyl suchas 3-furylmethyl and 2-furylethyl, furyl(lower)alkenyl such as3-furylvinyl and 2-furylallyl, halogen such as fluorine, chlorine,bromine, and iodine, nitro, cyano, lower alkylthio such as methylthio,ethylthio, and propylthio, --OR¹³ wherein R¹³ is hydrogen, lower alkylsuch as methyl, ethyl, and propyl, lower alkenyl such as vinyl, allyl,and 2-butenyl, lower alkynyl such as ethynyl, 2-propynyl, and 3-butynyl,lower alkanoyl such as acetyl, propionyl, and butyryl, phenyl, loweralkoxyphenyl such as 3-methoxyphenyl and 4-ethoxyphenyl, nitrophenylsuch as 3-nitrophenyl and 4-nitrophenyl, cyanophenyl such as2-cyanophenyl and 3-cyanophenyl, phenyl(lower)alkyl such as benzyl,phenethyl, and phenylpropyl, cyanophenyl(lower)alkyl such as3-cyanophenylmethyl and 4-cyanophenylethyl, benzoyl, tetrahydropyranyl,pyridyl, trifluoromethylpyridyl, pyrimidinyl, benzothiazolyl, quinolyl,benzoyl(lower)alkyl such as benzoylmethyl and benzoylethyl,benzenesulfonyl, or lower alkyl benzenesulfonyl such as toluenesulfonyl,--CH₂ --T--R¹⁴ wherein T is oxygen, sulfur or NR¹⁵ wherein R¹⁵ ishydrogen or lower alkyl and R¹⁴ is phenyl, halophenyl such as2-chlorophenyl and 4-fluorophenyl, lower alkylphenyl such as2-methylphenyl and 2,5-dimethylphenyl, lower alkoxyphenyl such as2-methoxyphenyl and 4-ethoxyphenyl, pyridyl, or pyrimidinyl, and thelike. Among those lower alkyl and halogenated alkyl are preferable, andmethyl is especially preferable.

Preferred embodiments of R¹ include pyridin-2-yl, pyridin-3-yl,isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 2-isoxazolin-3-yl,2-isoxazolin-5-yl, imidazol-2-yl, 1,3,4-oxadiazol-2-yl,1,2,4-oxadiazol-3-yl, and 1,2,3-thiadiazol-5-yl which are substitutedoptionally.

Especially preferred embodiments of R¹ include isoxazol-3-yl,5-methylisoxazol-3-yl, 3-methylisoxazol-5-yl, 2-isoxazolin-3-yl,1-methylimidazol-2-yl, and 1,3,4-oxadiazol-2-yl.

The aryl of the optionally substituted aryl represented by R² includesC6-C14 aryl such as phenyl, naphthyl (ex. 1-naphthyl and 2-naphthyl),and the like.

The optionally substituted heterocyclic group represented by R² includesan unsubstituted heterocyclic group and a substituted heterocyclicgroup. Examples of these heterocyclic groups are 5 to 7 memberedheterocyclic groups having 1 to 4 hetero atoms selected from nitrogen,sulfur, and oxygen in the ring, specifically, pyridyl such aspyridin-2-yl, pyridin-3-yl, and pyridin-4-yl, pyrimidinyl such aspyrimidin-2-yl, pyrimidin-4-yl, and pyrimidin-5-yl, benzoxazolyl such asbenzoxazol-2-yl, benzothiazolyl such as benzothiazol-2-yl,benzoimidazolyl, isoxazolyl such as isoxazol-3-yl and isoxazol-5-yl,isothiazolyl, thiadiazolyl such as 1,3,4-thiadiazolyl and1,2,4-thiadiazolyl, pyridazinyl, pyrrolyl, pyrazolyl, furyl such as2-furyl and 3-furyl, thienyl such as 2-thienyl and 3-thienyl,imidazolyl, oxazolyl, thiazolyl such as thiazol-2-yl, oxadiazolyl suchas 1,3,4-oxadiazolyl and 1,2,4-oxadiazolyl, triazolyl such as1,2,3-triazolyl and 1,2,4-triazolyl, quinolyl such as quinolin-2-yl,indolyl, benzisothiazolyl, benzisoxazolyl, pyrazinyl such aspyrazin-2-yl, morpholino, piperidino, piperazinyl, pyrrolidino,homopiperidino, quinazolinyl such as quinazolin-2-yl, and the like. Anyof these heterocyclic groups may form a fused ring with a carbocyclicring or another heterocyclic ring and may have a bond binding to M atany possible position on the ring.

The substituents of the substituted aryl and substituted heterocyclicgroup represented by R² include the same as being exemplified as thoseof the substituted heterocyclic group represented by R¹. Among those,halogen, lower alkyl, halogenated lower alkyl, lower alkoxy, halogenatedlower alkoxy, lower alkylthio, phenyl, and phenoxy are preferable.Halogen, lower alkyl, halogenated lower alkyl, lower alkoxy, andhalogenated lower alkoxy are more preferable. These substituents may beat any position possible to substitute on the ring. The number of thesubstituents, which may be the same or different from each other, is 1to 5, preferably 1 to 4, and more preferably 1 to 3.

R² preferably includes phenyl and a heterocyclic group unsubstituted orsubstituted with 1 to 3 substituents selected from the group consistingof halogen, lower alkyl, halogenated lower alkyl, lower alkoxy,halogenated lower alkoxy, lower alkylthio, phenyl, and phenoxy.

Preferred embodiments of R² include phenyl; phenyl having 1 to 3substituents selected from the group consisting of lower alkoxy(preferably methoxy), halogenated lower alkoxy (preferablytrifluoromethyloxy), halogenated lower alkyl (preferablytrifluoromethyl), halogen (preferably chlorine), and lower alkyl(preferably methyl), for example, 2-chlorophenyl, 3-chlorophenyl,4-chlorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl,2,5-dimethylphenyl, 3,4-dimethylphenyl, 4-chloro-2-methylphenyl,3,4-dichlorophenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl,4-methoxyphenyl, 3-trifluoromethyloxyphenyl, 4-trifluoromethyloxyphenyl,and the like; pyridyl substituted with halogen (preferably chlorine)and/or halogenated lower alkyl (preferably trifluoromethyl), forexample, 3,5-dichloropyridin-2-yl, 5-trifluoromethylpyridin-2-yl,5-trifluoromethyl-3-chloropyridin-2-yl,3-trifluoromethyl-5-chloropyridin-2-yl, and the like; morpholinosubstituted with lower alkyl (preferably methyl), for example,2,6-dimethylmorpholino and the like; and piperidino substituted withlower alkyl (preferably methyl), for example, 3,5-dimethylpiperidino andthe like.

The alkyl represented by R³ includes, for example, C1-C4 alkyl,preferably C1-C3 alkyl such as methyl, ethyl, propyl, isopropyl, and thelike.

The alkenyl represented by R³ includes, for example, C2-C6 alkenyl,preferably C3-C4 alkenyl such as allyl, 1-propenyl, isopropenyl,2-butenyl, isobutenyl, and the like.

The alkynyl represented by R³ includes, for example, C2-C6 alkynyl,preferably C2-C4 alkynyl such as 2-propynyl, 3-butynyl, and the like.

The preferred embodiment of R³ is alkyl, especially methyl.

The alkyl represented by R⁴ includes the same as those exemplified asalkyl represented by R³.

The alkoxy represented by R⁴ includes, for example, C1-C6 alkoxy,preferably C1-C4 alkoxy such as methoxy, ethoxy, propoxy, isopropoxy,butoxy, isobutoxy, sec-butoxy, tert-butoxy, and the like.

The halogen represented by R⁴ includes fluorine, chlorine, bromine, andiodine.

The halogenated alkyl represented by R⁴ includes C1-C6 alkyl, preferablyC1-C4 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, and thelike which are substituted with at least one halogen atom such asfluorine, chlorine, bromine, or iodine, for example, difluoromethyl,trifluoromethyl, chloromethyl, 2,3-dichloropropyl, and the like. Amongthose trifluoromethyl is preferable.

The preferred embodiment of R⁴ is hydrogen.

The alkyl represented by R⁵ to R¹² includes the same as thoseexemplified as alkyl represented by R³, preferably methyl or ethyl.

The acyl represented by R⁵ to R⁸, and R¹² includes alkanoyl, aroyl, andthe like. The alkanoyl includes alkanoyl having C1-C6 alkyl group,preferably C1-C4 alkyl group, for example, acetyl, trifluoroacetyl,propionyl, butyryl, and the like. Among those acetyl is preferable. Thearoyl includes C6-C14 aroyl, for example, benzoyl, naphthoyl, and thelike. Among those benzoyl is preferable.

The halogenated alkyl represented by R⁶, R⁸ to R¹¹ includes the same asthose exemplified as halogenated alkyl represented by R⁴. Among thosetrifluoromethyl is preferable.

The alkoxyalkyl represented by R⁶ and R⁸ includes alkoxyalkyl havingC1-C6 alkoxy, preferably C1-C4 alkoxy such as methoxymethyl,ethoxymethyl, methoxyethyl, and the like. Among those methoxymethyl ispreferable.

The alkyl of the alkylthio, alkylsulfinyl, and alkylsulfonyl representedby R⁶ and R⁸ includes the same as those exemplified as alkyl representedby R³. Among those methyl is preferable.

The optionally substituted amino represented by R⁶ and R⁸ includesamino, amino mono- or di-substituted with C1-C8 alkyl, preferably C1-C4alkyl (e.g., monomethylamino, dimethylamino, monoethylamino, etc.),amino mono-substituted with formyl, amino mono-substituted with C2-C8alkanoyl, preferably C2-C4 alkanoyl (e.g., methylcarbonylamino etc.),and the like.

The cycloalkyl represented by R⁶, R⁸, and R⁹ includes, for example,cycloalkyl having 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms,specifically cyclopropyl, cyclopentyl, cyclohexyl and the like.

The alkoxycarbonyl represented by R⁶ and R⁸ includes, for example,alkoxycarbonyl having C1-C6 alkyl, preferably C1-C4 alkyl, specificallymethoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, and the like.

When M is --Q--N═C(R⁶)--, R² and R⁶ taken together may form a monocyclicring or a fused polycyclic ring optionally having hetero atom(s). Themonocyclic ring is formed with the carbon atom to which R² and R⁶ arebound, includes a 4 to 8 membered ring optionally having hetero atom(s)such as oxygen, nitrogen, sulfur and the like, and may form a polycyclicring fused with another ring. Examples of the monocyclic ring and thefused polycyclic ring include cyclopentane, cyclohexane, indan,1,2,3,4-tetrahydronaphthalene, 5,6,7,8-tetrahydroquinoline,4,5,6,7-tetrahydrobenzo[b]furan, and the like. These rings may have adivalent bond at any possible position.

M preferably includes oxygen, --O--N═C(R⁶)--, --CH═N--N═C(R⁹)-- and--CH═N--O--(CR¹⁰ R¹¹)m--.

Preferred embodiments of M include oxygen, --O--N═C(CH₃)--,--O--N═C(SCH₃)--, --O--N═C(CN)--, --O--N═C(CF₃)--, --CH═N--N═C(CH₃)--,--CH═N--O--CH(CH₃)-- and --CH═N--O--C(CH₃)₂ --.

The compounds of this invention have asymmetric carbon at the a positionof the benzyl group and include each optical isomer and a mixture ofthese isomers in any ratio.

Examples of the compounds represented by the formula (I) includecompounds shown in the examples described below. For example, thefollowing compounds (the compound numbers are coincident with thosenumbered in the examples described below.) are preferable.

A compound (compound number A-12) wherein R¹ is 3-methylisoxazol-5-yl,R² is 2-methylphenyl, R³ is methyl, R⁴ is hydrogen, M is oxygen and n is1;

a compound (compound number A-36) wherein R¹ is 3-methylisoxazol-5-yl,R² is 2,5-dimethylphenyl, R³ is methyl, R⁴ is hydrogen, M is oxygen andn is 1;

a compound (compound number A-55) wherein R¹ is 3-methylisoxazol-5-yl,R² is 2,3,5-trimethylphenyl, R³ is methyl, R⁴ is hydrogen, M is oxygenand n is 1;

a compound (compound number A-69) wherein R¹ is 3-methylisoxazol-5-yl,R² is 5-trifluoromethyl-3-chloropyridin-2-yl, R³ is methyl, R⁴ ishydrogen, M is oxygen and n is 1;

a compound (compound number A-102) wherein R¹ is 3-methylisoxazol-5-yl,R² is 3-trifluoromethylphenyl, R³ is methyl, R⁴ is hydrogen, M is--O--N═C(CH₃)-- and n is 1;

a compound (compound number A-103) wherein R¹ is 3-methylisoxazol-5-yl,R² is 4-trifluoromethylphenyl, R⁸ is methyl, R⁴ is hydrogen, M is--O--N═C(CH₃)-- and n is 1;

a compound (compound number A-323) wherein R¹ is 3-methylisoxazol-5-yl,R² is 2,6-dimethylmorpholino, R³ is methyl, R⁴ is hydrogen, M is--O--N═C(CH₃)-- and n is 1;

a compound (compound number A-327) wherein R¹ is 3-methylisoxazol-5-yl,R² is 3,5-dimethylpiperidino, R³ is methyl, R⁴ is hydrogen, M is--O--N═C(CH₃)-- and n is 1;

a compound (compound number A-373) wherein R¹ is 3-methylisoxazol-5-yl,R² is 4-trifluoromethylphenyl, R³ is methyl, R⁴ is hydrogen, M is--CH═N--O--CH(CH₃)-- and n is 0;

a compound (compound number A-385) wherein R¹ is 3-methylisoxazol-5-yl,R² is 4-chlorophenyl, R³ is methyl, R⁴ is hydrogen, M is--CH═N--N═C(CH₃)-- and n is 0;

a compound (compound number A-386) wherein R¹ is 3-methylisoxazol-5-yl,R² is 4-bromophenyl, R³ is methyl, R⁴ is hydrogen, M is--CH═N--N═C(CH₃)-- and n is 0;

a compound (compound number A-388) wherein R¹ is 3-methylisoxazol-5-yl,R² is 4-methylphenyl, R³ is methyl, R⁴ is hydrogen, M is--CH═N--N═C(CH₃)-- and n is 0;

a compound (compound number A-393) wherein R¹ is 3-methylisoxazol-5-yl,R² is 4-trifluoromethylphenyl, R³ is methyl, R⁴ is hydrogen, M is--CH═N--N═C(CH₃)-- and n is 0;

a compound (compound number A-504) wherein R¹ is 3-methylisoxazol-5-yl,R² is 3-trifluoromethyloxyphenyl, R³ is methyl, R⁴ is hydrogen, M is--CH═N--N═C(CH₃)-- and n is 0;

a compound (compound number A-505) wherein R¹ is 3-methylisoxazol-5-yl,R² is 4-trifluoromethyloxyphenyl, R³ is methyl, R⁴ is hydrogen, M is--CH═N--N═C(CH₃)-- and n is 0;

a compound (compound number D-36) wherein R¹ is isoxazol-3-yl, R² is2,5-dimethylphenyl, R³ is methyl, R⁴ is hydrogen, M is oxygen and n is1;

a compound (compound number D-41) wherein R¹ is isoxazol-3-yl, R² is4-chloro-2-methylphenyl, R³ is methyl, R⁴ is hydrogen, M is oxygen and nis 1;

a compound (compound number D-65) wherein R¹ is isoxazol-3-yl, R² is3,5-dichloropyridin-2-yl, R³ is methyl, R⁴ is hydrogen, M is oxygen andn is 1;

a compound (compound number D-103) wherein R¹ is isoxazol-3-yl, R² is4-trifluoromethylphenyl, R³ is methyl, R⁴ is hydrogen, M is--O--N═C(CH₃)-- and n is 1;

a compound (compound number E-36) wherein R¹ is 5-methylisoxazol-3-yl,R² is 2,5-dimethylphenyl, R³ is methyl, R⁴ is hydrogen, M is oxygen andn is 1;

a compound (compound number E-396) wherein R¹ is 5-methylisoxazol-3-yl,R² is 3,4-dichlorophenyl, R³ is methyl, R⁴ is hydrogen, M is--CH═N--N═C(CH₃)-- and n is 0;

a compound (compound number E-505) wherein R¹ is 5-methylisoxazol-3-yl,R² is 4-trifluoromethyloxyphenyl, R³ is methyl, R⁴ is hydrogen, M is--CH═N--N═C(CH₃)-- and n is 0;

a compound (compound number I-12) wherein R¹ is 1-methylimidazol-2-yl,R² is 2-methylphenyl, R³ is methyl, R⁴ is hydrogen, M is oxygen and n is1; and

a compound (compound number I-41) wherein R¹ is 1-methylimidazol-2-yl,R² is 4-chloro-2-methylphenyl, R³ is methyl, R⁴ is hydrogen, M is oxygenand n is 1.

The compound (I) of this invention (Namely, the compound represented bythe formula (I). The compounds represented by the other formulas may beabbreviated in the same manner.) can, for example, be manufacturedaccording to the following synthesis routes.

Route 1 ##STR2## wherein X is lithium or magnesium halide (ex. --MgBr,MgI and so on) and the other symbols are the same as above.

The compound represented by the formula (IV) can be manufactured byreacting the compound (II) with the compound (III) in an appropriatepure or mixed solvent.

The amount of the compound (III) to be used in this reaction is at leastone equivalent to the compound (II), preferably 1 to 3 equivalents toit.

The solvent to be used includes aromatic hydrocarbons such as toluene,benzene, xylene etc., saturated hydrocarbons such as cyclohexane, hexaneetc., ethers such as tetrahydrofuran, diethyl ether, dioxane etc.,triethylamine, and the mixed solvents of these.

The reaction temperature is -90 to 100° C., preferably -70 to 40° C. Thereaction time varies with the compound to be used and may be 0.5 to 80hours.

The compound (IV) obtained in this reaction is novel and one of theobjects of this invention.

The compound (IV) can be used in the following step as a crude productor after being purified by the conventional methods such as columnchromatography, recrystallization, etc.

The compound (II) used as starting material in this reaction can beprepared by reacting a compound which part corresponding to X is halogenwith butyllithium or magnesium according to the methods of JP-A 3-246268or JP-A 5-97768.

Route 1 (continued) ##STR3## wherein L is halogen such as chlorine,bromine, iodine and the like, alkylsulfonyloxy such as loweralkylsulfonyloxy (ex. methanesulfonyloxy, ethanesulfonyloxy and thelike), arylsulfonyloxy optionally substituted with halogen or loweralkyl such as benzenesulfonyloxy, p-toluenesulfonyloxy,m-toluenesulfonyloxy, o-toluenesulfonyloxy and the like oralkoxysulfonyloxy such as lower alkoxysulfonyloxy (ex.methoxysulfonyloxy, ethoxysulfonyloxy and the like) and other symbolsare the same as defined above.

The compound of this invention represented by the formula (I) can beprepared by reacting the compound (IV) with the compound (V) in thepresence of a base in an appropriate, pure or mixed solvent.

The amount of the compound (V) may be at least one equivalent,preferably 1 to 2 equivalents to the compound (IV) in this reaction.

Examples of the bases to be used are metal hydroxides such as sodiumhydroxide, potassium hydroxide and the like, metal hydrides such assodium hydride, potassium hydride and the like and metal alkoxides suchas sodium methoxide, sodium ethoxide, potassium tert-butoxide and thelike. The amount of the base may be at least one equivalent, preferably1 to 2 equivalents to the compound (IV).

Examples of the solvents to be used are N,N-dimethylformamide,dimethylsulfoxide, aromatic hydrocarbons such as toluene, benzene,xylene and the like, saturated hydrocarbons such as cyclohexane, hexaneand the like, ethers such as tetrahydrofuran, dioxane and the like,ketones such as acetone, methyl ethyl ketone and the like, water and themixed solvents of these.

The reaction temperature is -30 to 150° C., preferably -10 to 100° C.The reaction time varies with compounds to be used and may be 0.5 to 90hours.

The desired compound (I) thus obtained may be purified by theconventional methods such as column chromatography, recrystallizationand the like, if necessary.

[Route 2] ##STR4## wherein each symbol is as defined above.

The compound represented by the formula (IV) can be prepared by reducingthe compound (VI).

Examples of the reducing agents to be used are metal hydrides such aslithium aluminum hydride, sodium borohydride and the like. The molarratio of the reducing agent to be used may be at least 0.25, preferably0.25 to 1.5 to the compound (VI).

The reaction temperature is -80 to 150° C., preferably -20 to 100° C.The reaction time varies with the compounds to be used and may be 0.5 to90 hours.

Examples of the solvents to be used are ethers such as ethyl ether,tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethyleneglycol dimethyl ether and the like, aromatic hydrocarbons such astoluene, benzene, xylene and the like and the mixed solvents of thesewhere the reducing agent is lithium aluminum hydride, and alcohol suchas methanol, ethanol, isopropanol and the like, aromatic hydrocarbonssuch as toluene, benzene, xylene and the like, ethers such astetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycoldimethyl ether and the like, N,N-dimethylformamide, dimethylsulfoxide,water and the mixed solvents of these where the reducing agent is sodiumborohydride.

The compound (IV) may be used in the next step as a crude product orafter purified by the conventional methods such as chromatography,recrystallization and the like.

The compound (VI) to be used as a starting material in this reaction maybe prepared by reacting the compound (II) with reactive derivatives ofcarboxylic acid having an optionally substituted heterocyclic ring (R¹)according to the method of Japanese patent application No. 6-87819.

[Route 3] ##STR5## wherein P is a protecting group of a hydroxyl groupand the other symbols are as defined above.

The compound represented by the formula (VIII) can be prepared byreducing the compound (VII).

The protecting group represented by P includes, for example, alkyl suchas tert-butyl and the like, aralkyl such as triphenylmethyl and thelike, trialkylsilyl such as tert-butyldimethylsilyl, triisopropylsilyland the like, alkyldiarylsilyl such as tert-butyldiphenylsilyl and thelike, triaralkylsilyl such as tribenzylsilyl and the like, alkoxyalkylsuch as methoxymethyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl and thelike, alkoxyalkoxyalkyl such as -methoxyethoxymethyl and the like,alkylthioalkyl such as methylthiomethyl and the like, tetrahydropyranylsuch as tetrahydropyran-2-yl, 4-methoxytetrahydropyran-4-yl and thelike, tetrahydrothiopyranyl such as tetrahydrothiopyran-2-yl and thelike, tetrahydrothiofuranyl such as tetrahydrothiofuran-2-yl and thelike and aralkyloxyalkyl such as benzyloxymethyl and the like.

The amount and type of the reducing agents and the solvents to be usedand the reaction temperature and time are the same as described in theabove Scheme 3.

The compound (VIII) may be used in the next step as a crude product orafter purified by the conventional methods such as chromatography,recrystallization and the like.

The compound (VII) used in this reaction as a starting material may beprepared according to the method disclosed in Japanese patentapplication No. 6-87819, for example, the same method as that forpreparing the compound (VI).

[Route 3 (continued)] ##STR6## wherein each symbol is as defined above.

The compound represented by the formula (IX) can be prepared by reactingthe compound (VIII) with the compound (V) in an appropriate pure ormixed solvent in the presence of a base.

The base and solvent to be used and the reaction temperature and timemay be the same as those described in the above Scheme 2.

The compound (IX) may be used in the next step as a crude product orafter purified by the conventional methods such as chromatography,recrystallization and the like.

[Route 3 (continued)] ##STR7## wherein each symbol is as defined above.

The compound (X) can be prepared by deprotecting the protecting group ofthe hydroxyl group of the compound (IX).

The deprotection of the hydroxyl group can be done by the conventionalmethods such as those described in T. W. Green, Protective Groups inOrganic Synthesis, p.1˜113, John Willy & Sons (1981); C. B. Reese,Protective Groups in Organic Chemistry, J. F. McOmie, p.95˜143, PlenumPress (1973).

For example, the deprotection can be achieved by treating the compound(IX) with an acid in an appropriate solvent.

Examples of the acid to be used include inorganic acids such ashydrohalogenic acids (ex. hydrochloric acid, hydrobromic acid,hydroiodic acid and the like), hydrogen halogenides (ex. hydrogenchloride, hydrogen bromide, hydrogen iodide and the like), boric acid,phosphoric acid, sulfuric acid and the like, sulfonic acids (ex.aliphatic sulfonic acids such as trifluoromethanesulfonic acid, aromaticsulfonic acids such as toluenesulfonic acid, their pyridinium salts andthe like), carboxylic acids (ex. acetic acid, trifluoroacetic acid andthe like), silica gel, and Lewis acid (ex. aluminum halogenides such asaluminum chloride, zinc chloride, titanium tetrachloride and the like).One or more of acids may appropriately be selected from these to beused.

The amount of the acid to be used is a trace to 1 equivalent to thecompound (IX), or carboxylic acids may be used as a solvent.

The solvent to be used varies with the reaction conditions and mayinclude hydrocarbons such as benzene, toluene, xylene and the like,halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane andthe like, ethers such as tetrahydrofuran, dioxane and the like, alcoholssuch as methanol, ethanol and the like, nitrites such as acetonitrileand the like, water and their mixed solvents.

The reaction temperature is -80 to 150° C., preferably -10 to 80° C. Thereaction time is 1 minute to 4 hours, preferably 5 minutes to 2 hours.

Where the protecting group is substituted silyl, the deprotection can bedone under the basic condition (ex. in sodium hydroxide/hydrous ethanoland the like) or in the presence of fluoride anion (ex. n-Bu₄ N⁺ F⁻, C₅H₅ N⁺ HF⁻ and the like).

The compound (X) thus obtained is novel and one of the objects of thisinvention. The compound (X) may be used in the next step as the reactionmixture itself or a crude product or after purified by the conventionalmethods such as chromatography, recrystallization and the like.

[Route 3 (continued)] ##STR8## wherein each symbol is as defined above.

The compound of this invention represented by the formula (Ia) can beprepared by allowing the compound (X) to react with the compound (XI) inan appropriate pure or mixed solvent in the presence of a base.

The amount of the compound (XI) to be used in this reaction is 1 or moreequivalents to the compound (X), preferably 1 to 2 equivalents.

The bases to be used include, for example, metal hydrides such as sodiumhydride, potassium hydride etc., metal hydroxides such as sodiumhydroxide, potassium hydroxide etc., metal carbonates such as sodiumcarbonate, potassium carbonate etc., and metal alkoxides such as sodiummethoxide, sodium ethoxide, potassium tert-butoxide etc. The amount ofthe base to be used is 1 or more equivalents to the compound (X),preferably 1 to 3 equivalents.

The solvents to be used include, for example, N,N-dimethylformamide,dimethylsulfoxide, aromatic hydrocarbons such as toluene, benzene,xylene etc., saturated hydrocarbons such as cyclohexane, hexane etc.,halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethaneetc., ethers such as tetrahydrofuran, dioxane etc., ketones such asacetone, methyl ethyl ketone etc., nitrites such as acetonitrile etc.,water, and their mixed solvents.

The reaction temperature is 0 to 190° C., preferably 10 to 160° C. Thereaction time varies with the compound to be used and may be 0.5 to 90hours.

The compound (Ia) thus obtained can be purified by the conventionalmethods such as column chromatography, recrystallization etc. ifnecessary.

[Route 4] ##STR9## wherein Y is halogen such as chlorine, bromine or thelike, and the other symbols are as defined above.

The compound represented by the formula (XII) can be prepared byreacting the compound (Xa) with a halogenating agent in an appropriatepure or mixed solvent or without any solvent.

The halogenating agents to be used include, for example, thionyl halidessuch as thionyl chloride, thionyl bromide etc., phosphoryl halides suchas phosphoryl chloride, phosphoryl bromide etc., phosphorus halides suchas phosphorus pentachloride, phosphorous trichloride, phosphoruspentabromide, phosphorus tribromide etc., carbon oxychloride, oxalylhalides such as oxalyl chloride etc., triphenylphosphinelcarbontetrachloride, and triphenylphosphine/carbon tetrabromide. The amount tobe used is 1 or more equivalents to the compound (Xa).

The solvents to be used include, for example, aromatic hydrocarbons suchas toluene, benzene, xylene etc., saturated hydrocarbons such ascyclohexane, hexane etc., halogenated hydrocarbons such asdichloromethane, 1,2-dichloroethane etc., nitrites such as acetonitrileetc., and their mixed solvents.

The reaction temperature is -30 to 150° C., preferably -10 to 120° C.The reaction time varies with the compound to be used and may be 0.1 to48 hours.

The compound (XII) thus obtained is novel and is one of the objects ofthis invention. The compound (XII) can be used in the following step asa crude product or after purified by the conventional methods such ascolumn chromatography, recrystallization etc.

[Route 4 (continued)] ##STR10## wherein each symbol is as defined above.

The compound of this invention represented by the formula (Ib) can beprepared by reacting the compound (XII) with the compound (XIII) in thepresence of a base in an appropriate pure or mixed solvent or withoutany solvent.

The amount of the compound (XIII) to be used in this reaction is 1 ormore equivalents to the compound (XII).

The bases to be used include, for example, metal hydrides such as sodiumhydride, potassium hydride etc., metal hydroxides such as sodiumhydroxide, potassium hydroxide etc., metal carbonates such as sodiumcarbonate, potassium carbonate etc., and metal alkoxides such as sodiummethoxide, sodium ethoxide, potassium tert-butoxide etc. The amount ofthe base to be used is 1 or more equivalents to the compound (XII),preferably 1 to 3 equivalents.

The solvents to be used include, for example, N,N-dimethylformamide,dimethylsulfoxide, aromatic hydrocarbons such as toluene, benzene,xylene etc., saturated hydrocarbons such as cyclohexane, hexane etc.,halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethaneetc., ethers such as tetrahydrofuran, dioxane etc., ketones such asacetone, methyl ethyl ketone etc., nitriles such as acetonitrile etc.,water, and their mixed solvents.

The reaction temperature is 0 to 190° C., preferably 10 to 160° C. Thereaction time varies with the compound to be used and may be 0.5 to 90hours.

The compound (Ib) thus obtained can be purified by the conventionalmethods such as column chromatography, recrystallization etc. ifnecessary.

[Route 5] ##STR11## wherein each symbol is as defined above.

The benzoic aldehydes represented by the formula (XIV) can be preparedby oxidizing the compound (Xa) with an oxidizing agent.

The oxidizing agents to be used include, for example, pyridiniumchlorochromate, tert-butyl chromate, nickel peroxide, activateddimethylsulfoxide and the like.

In the case of the Swern oxidization, one of the known activateddimethylsulfoxide oxidization methods using activated dimethylsulfoxide,the amounts of dimethylsulfoxide and oxalyl chloride as an electrophilicreagent to be used each is 1 or more equivalents to the compound (Xa),preferably 1 to 4 equivalents.

The solvents to be used include, for example, halogenated hydrocarbonssuch as dichloromethane etc.

The reaction temperature is -78 to -20° C., preferably -78 to -40° C.The reaction time varies with the compound to be used and may be 15minutes to 3 hours.

Then, a base such as triethylamine is added to form sulfonium ylide.

The amount of the base to be used is 1 or more equivalents to thecompound (Xa), preferably 1 to 6 equivalents.

The reaction temperature is -78 to -50° C., preferably -78 to -30° C.The reaction time varies with the compound to be used and may be 15minutes to 3 hours.

After the reaction, water is added thereto and the resulting product isextracted with a solvent. The compound (XIV) thus obtained can be usedin the following step as a crude product or after purified by theconventional methods such as column chromatography, recrystallizationetc. if necessary.

[Route 5 (continued)] ##STR12## wherein W is --N═C(R⁹)-- (R⁹ is asdefined above.) or --A--(CR¹⁰ R¹¹)m-- (A, R¹⁰, R¹¹ and m are as definedabove.) and the other symbols are as defined above.

The compound of this invention represented by the formula (Ic) can beprepared by reacting the compound (XIV) with the compound (XV),derivatives of hydrazone, O-substituted hydroxylamine or hydrazine, orits salt such as hydrochloride or sulfate in an appropriate pure ormixed solvent.

The amount of the compound (XV) to be used in this reaction is 1 or moreequivalents to the compound (XIV), preferably 1 to 3 equivalents.

The solvents to be used include, for example, aromatic hydrocarbons suchas toluene, benzene, xylene etc., saturated hydrocarbons such ascyclohexane, hexane etc., alcohols such as methanol, ethanol, propanoletc., ethers such as tetrahydrofuran, dioxane etc., water, and theirmixed solvents.

The reaction temperature is 0 to 160° C., preferably 20 to 130 °. Thereaction time varies with the compound to be used and may be 0.5 to 90hours.

The compound (Ic) thus obtained can be purified by the conventionalmethods such as column chromatography, recrystallization etc. ifnecessary.

The hydrazone derivatives of the compound (XV) to be used in thisreaction as a starting material can be prepared by reacting thecorresponding ketone derivatives with hydrazine.

Some of the O-substituted hydroxylamine derivatives of the compound (XV)are known and the other can be prepared by the known method similar tothat described in Methoden der Organischen Chemie, X/1, Houben-Weyl.

Some of the hydrazine derivatives of the compound (XV) are known and theother can be prepared by the known method similar to that described inMethoden der Organischen Chemie, X/2, Houben-Weyl.

[Route 6] ##STR13## wherein each symbol is as defined above.

The compound (XVI) can be prepared by reacting the compound (XIV) withhydroxylamine or its salt in an appropriate solvent.

The amount of the hydroxylamine to be used is 1 to 4 equivalents to thecompound (XIV), preferably 1 to 2.5 equivalents.

The salts of hydroxylamine include, for example, mineral acid salts suchas hydrochloride, sulfate and so on. The salt is neutralized with a baseto be used in this reaction. The bases to be used include, for example,metal hydroxides such as sodium hydroxide, potassium hydroxide etc.,metal carbonates such as sodium carbonate, potassium carbonate etc.,metal alkoxides such as sodium methoxide, sodium ethoxide etc., andpyridine, etc. The amount of the base to be used is 1 to 3 equivalentsto the hydroxylamine salt, preferably 1 to 2 equivalents.

The solvents to be used include, for example, aromatic hydrocarbons suchas toluene, benzene, xylene etc., halogenated hydrocarbons such aschloroform, 1,2-dichloroethane etc., ethers such as tetrahydrofuran,dioxane etc., alcohols such as methanol, ethanol, n-propanol,isopropanol etc., water, and their mixed solvents. The reactiontemperature is 0 to 150° C., preferably 20 to 100° C. The reaction timevaries with the compound to be used and may be 15 minutes to 24 hours.

The compound (XVI) thus obtained can be used in the following step asthe reaction solution itself or a crude product or after being purifiedby the conventional methods such as column chromatography,recrystallization etc.

[Route 6 (continued)] ##STR14## wherein each symbol is as defined above.

The compound of this invention represented by the formula (Id) can beprepared by reacting the compound (XVI) with the compound (XVII) in thepresence of a base in an appropriate pure or mixed solvent or withoutany solvent.

The amount of the compound (XVII) to be used in this reaction is 1 ormore equivalents to the compound (XVI).

The bases to be used include, for example, metal hydrides such as sodiumhydride, potassium hydride etc., metal hydroxides such as sodiumhydroxide, potassium hydroxide etc., metal carbonates such as sodiumcarbonate, potassium carbonate etc., and metal alkoxides such as sodiummethoxide, sodium ethoxide, potassium tert-butoxide etc. The amount ofthe base to be used is 1 or more equivalents, preferably 1 to 2equivalents.

The solvents to be used include, for example, N,N-dimethylformamide,dimethylsulfoxide, aromatic hydrocarbons such as toluene, benzene,xylene etc., saturated hydrocarbons such as cyclohexane, hexane etc.,halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethaneetc., ethers such as tetrahydrofuran, dioxane etc., ketones such asacetone, methyl ethyl ketone etc., nitrites such as acetonitrile etc.,water, and their mixed solvents.

The reaction temperature is -30 to 120° C., preferably 0 to 90° C. Thereaction time varies with the compound to be used and may be 0.5 to 90hours.

The compound (Id) thus obtained can be purified by the conventionalmethods such as column chromatography, recrystallization etc. ifnecessary.

[Route 7] ##STR15## wherein R¹⁶ is alkyl (ex. lower alkyl such asmethyl, ethyl and propyl) and the other symbols are as defined above.

The compound represented by the formula (XIX) can be prepared byreacting the compound (XVIII) with hydrazine monohydrate or hydrazinesalt such as hydrochloride and sulfate in an appropriate pure or mixedsolvent.

The amount of hydrazine to be used in this reaction is 1 or moreequivalents to the compound (VIII), preferably 1 to 7 equivalents.

The solvents to be used include, for example, aromatic hydrocarbons suchas toluene, benzene, xylene etc., saturated hydrocarbons such ascyclohexane, hexane etc., alcohols such as methanol, ethanol, propanoletc., ethers such as tetrahydrofuran, dioxane etc., water, and theirmixed solvents.

The reaction temperature is 0 to 160° C., preferably 10 to 130° C. Thereaction time varies with the compound to be used and may be 0.5 to 90hours.

The compound (XIX) thus obtained can be used in the following step asthe reaction solution itself or a crude product or after being purifiedby the conventional methods such as column chromatography,recrystallization etc.

The compound (XVIII) to be used in this reaction as a starting materialcan be prepared by, for example, reducing the correspondingα-ketocarboxylate ester followed by alkylation, alkenylation oralkynylation according to the method described in PCT/JP95100663.

[Route 7 (continued)] ##STR16## wherein R¹⁷ and R¹⁸ each is alkyl (ex.lower alkyl such as methyl, ethyl and propyl) and the other symbols areas defined above.

The compound of this invention represented by the formula (Ie) can beprepared by reacting the compound (XIX) with the compound (XX) in thepresence or absence of an acid in an appropriate pure or mixed solventor without any solvent according to the method of C. Ainaworth, J. Am.Chem. Soc., 77, 1148 (1955).

The amount of the compound (XX) to be used in this reaction is 1 or moreequivalents to the compound (XIX), preferably 1 to 20 equivalents.

The acid to be used includes, for example, hydrogen halides such ashydrogen chloride, hydrogen bromide, hydrogen iodide etc., and sulfonicacids (ex. aliphatic sulfonic acid such as trifluoromethanesulfonic acidand aromatic sulfonic acid such as toluenesulfonic acid).

The amount of the acid to be used is a trace to 1 equivalent to thecompound (XIX).

The solvents to be used include, for example, aromatic hydrocarbons suchas toluene, benzene, xylene etc., saturated hydrocarbons such ascyclohexane, hexane etc., ethers such as tetrahydrofuran, dioxane etc.,and their mixed solvents.

The reaction temperature is 20 to 200° C., preferably 50 to 170° C. Thereaction time varies with the compound to be used and may be 0.5 to 90hours.

The compound (Ie) thus obtained can be purified by the conventionalmethods such as column chromatography, recrystallization etc. ifnecessary.

The compound (I) of this invention is effective against pathogenicmicrobes (fungi) and soil fungi on crop plants or their seeds such asrice, wheat, barley, rye, corn, millet, foxtail millet, buckwheat,soybean, redbean, peanut, etc., fruit trees such as citrus fruits,grape, apple, pear, peach, etc., or vegetables such as cucumber,eggplant, tomato, pumpkin, kidney bean, etc. The compound of thisinvention shows potent fungicidal activity particularly againstPyricularia oryzae, Rhizoctonia solani, Erysiphe graminis, Sphaerothecafuliginea, Erysiphe cichoracearum, Phylophthora infestans,Pseudoperonospora cubensis, Peronospora manshurica, Plasaopara viticola,Botrytis cinerea of vegetables, grape and so on, Pythium aphanidermatum,Sclerotinia sclerotiorum of buckwheat, soybean, colza and so on,Corticium rolfsii of soybean, redbean, potato, peanut and so on,Pseudocercosporella herpotrichoides and so on. Therefore, the compound(I) of this invention is useful as fungicides, particularly asagricultural fungicides.

The compound (I) of this invention also shows potent insecticidalactivity on injurious insects to plants. Particularly, it shows potentpreventing activity against insects such as Myzus persicae etc. injuringplants. Therefore, the compound (I) of this invention is also useful asinsecticides.

Application of the compound (I) of this invention as fungicides may bemade to plants by any conventional procedure such as atomizing,scattering or spreading of the active compound. Application may also bemade through treatment of seeds of plants, soil where plants grow, soilfor seeding, paddy field or water for perfusion with the activecompound. Application may be performed before or after the infectionwith phytopathogenic fungi on plants.

Application of the compound (I) of this invention as insecticides may bemade to insects by any conventional procedure such as atomizing,scattering or spreading of the active compound. In order to preventinjuries by insects, application of the compound (I) of this inventionmay also be made to plants by any conventional procedure such asatomizing, scattering or spreading of the active compound. Further,application may be made through treatment of seeds of plants, soil whereplants grow, soil for seeding, paddy field or water for perfusion withthe active compound.

The compound can be used in a conventional formulation form suitable foragricultural fungicides and insecticides such as solutions, wettablepowders, emulsions, suspensions, concentrated liquid preparations,tablets, granules. aerosols, powders, pastes, fumigants, flowable, etc.

Such formulation form can be prepared in a conventional manner by mixingat least one compound of this invention with an appropriate solid orliquid carrier(s) and, if necessary, an appropriate adjuvant(s) (e.g.,surfactants, spreaders, dispersants, stabilizers, etc.) for improvingthe dispersibility and other properties of the active ingredient.

Examples of the solid carriers or diluents include botanical materials(e.g., flour, tobacco stalk powder, soybean powder, walnut-shell powder,vegetable powder, saw dust, bran, bark powder, cellulose powder,vegetable extract residue, etc.), fibrous materials (e.g., paper,corrugated cardboard, old rags, etc.), artificial plastic powders, clays(e.g., kaolin, bentonite, fuller's earth, etc.), talc, other inorganicmaterials (e.g., pyrophyllite, sericite, pumice, sulfur powder, activecarbon, etc.), chemical fertilizers (e.g., ammonium sulfate, ammoniumphosphate, ammonium nitrate, urea, ammonium chloride, etc.), etc.

Examples of the liquid carriers or diluents include water, alcohols(e.g., methanol, ethanol, etc.), ketones (e.g., acetone, ethyl methylketone, etc.), ethers (e.g., diethyl ether, dioxane, cellosolve,tetrahydrofuran, etc.), aromatic hydrocarbons (e.g., benzene, toluene,xylene, methylnaphthalene, etc.), aliphatic hydrocarbons (e.g.,gasoline, kerosene, lamp oil, etc.), esters, nitriles, acid amides(e.g., N,N-dimethylformamide, N,N-dimethylacetamide, etc.), halogenatedhydrocarbons (e.g., dichloroethane, carbon tetrachloride, etc.), etc.

Examples of the surfactants include alkyl sulfates, alkyl sulfonates,alkylaryl sulfonates, polyethylene glycol ethers, polyhydric alcoholesters, etc.

Examples of the spreaders or dispersants include casein, gelatin, starchpowder, carboxymethyl cellulose, gum arabic, alginic acid, lignin,bentonite, molasses, polyvinyl alcohol, pine oil, agar, etc. Examples ofthe stabilizers include PAP (a mixture of isopropylphosphate), tricresylphosphate (TCP), tall oil, epoxidized oil, surfactants, fatty acids andtheir esters, etc.

The composition of the present invention may contain other fungicides,insecticides, herbicides or fertilizers in addition to the aboveingredients.

In general the above composition contains at least one compound of theformula (1) of the present invention in a concentration of 0.1 to 95% byweight, preferably 1.0 to 80% by weight. The composition can be used assuch or in a diluted form. About 1 g to 5 kg/hectare, preferably about10 g to 1.0 Kg/hectare, of the compound of the present invention is usedin a concentration of normally about 1 to 5,000 ppm, preferably about 10to 1,000 ppm.

EXAMPLES

The following Examples and Test Examples further illustrate the presentinvention in detail, but are not to be construed to limit the scopethereof. The ¹ H-NMR (CDCl₃) data in Examples were determined at 270 or400 MHz in CDCl₃ using tetramethylsilane as an internal standard andindicated in δ values (ppm). The coupling constants (J) are indicated inHz. In the data, s is a singlet, d is a doublet, t is a triplet, q is aquartet, quint is a quintet sept is a septet, m is a multiplet, and brsis a broad singlet .

Example 1

Synthesis of 2-[2-(2,5-dimethylphenoxymethyl)-α-hydroxybenzyl]pyridine(Compound No. IV-21)

A mixture of 2.91 g (0.01 mol) of 1-bromo-2-(2,5-dimethylphenoxymethyl)benzene and 8 ml of THF was added to a suspension of 0.36 g (0.015 mol)of magnesium, 0.1 ml of bromoethane, and 2 ml of tetrahydrofuran at 45to 55° C. over 5 minutes under a nitrogen gas atmosphere and stirred at50 to 55° C. for an hour to prepare a Grignard's reagent. The Grignard'sreagent was added to a mixture of 1.18 g (0.011 mol) of2-pyridinecarboxyaldehyde and 10 ml of THF below 5° C. over 15 minutesand stirred at room temperature for 2 hours. After completion of thereaction, 150 ml of an aqueous solution of ammonium chloride was addedand extracted with 150 ml of ether. After the extract was dried overanhydrous magnesium sulfate and concentrated under reduced pressure, theresidue thus obtained was purified by column chromatography on silicagel (ethyl acetate/n-hexane) to give 2.42 g of2-[2-(2,5-dimethylphenoxymethyl)-α-hydroxybenzyl]pyridine (75.8% yield)as colorless oil.

¹ H-NMR (CDCl₃) δ ppm: 2.16 (3H, s), 2.29 (3H, s), 4.96 (1H, d, J=11.6),5.32 (1H, d, J=11.6), 5.33 (1H, s), 6.05 (1H, d, J=1.8), 6.64 (1H, s),6.67 (1H, d, J=7.3), 7.00 (1H, d, J=7.3), 7.16-7.64 (7H, m), 8.57 (1H,dd, J=4.9, 1.8).

Example 2

Synthesis of 2-[2-(2,5-dimethylphenoxymethyl)-α-methoxybenzyl]pyridine(Compound No. J-36)

To a mixture of 0.42 g (1.3 mmol) of2-[2-(2,5-dimethylphenoxymethyl)-α-hydroxybenzyl]pyridine, 4 ml ofN,N-dimethylformamide and 0.12 ml (2 mmol) of methyl iodide was added0.07 g (1.7 mmol) of 60% sodium hydride under ice-cooling and stirred atthe same temperature for 3 hours. After completion of the reaction, 100ml of ether was added and washed twice with 80 ml of brine. The etherlayer was dried over anhydrous magnesium and concentrated under reducedpressure. The residue was purified by column chromatography on silicagel (ethyl acetate/n-hexane) to give2-[2-(2,5-dimethylphenoxymethyl)-α-methoxybenzyl]pyridine (0.40 g,92.3%) as colorless oil.

¹ H-NMR (CDCl₃) δ ppm: 2.19 (3H, s), 2.29 (3H, s), 3.45 (3H, s), 5.13(1H, d, J=12.3), 5.27 (1H, d, J=12.3), 5.67 (1H, s), 6.65 (1H, s), 6.67(1H, d, J=7.3), 7.01 (1H, d, J=7.3), 7.12-7.69 (7H, m), 8.53 (1H, dd,J=4.9, 1.8).

Example 3

Synthesis of2-[2-(4-chloro-2-methylphenoxymethyl)-α-hydroxybenzyl]-1-methylimidazole(Compound No. IV-17)

To a mixture of 1.02 g (3 mmol) of2-(4-chloro-2-methylphenoxymethyl)phenyl 1-methylimidazol-2-yl ketone, 6ml of tetrahydrofuran and 3 ml of methanol was added 0.11 g (3 mmol) ofsodium borohydride under ice-cooling and stirred at room temperature foran hour. After completion of the reaction, 100 ml of brine was added andextracted twice with 50 ml of dichloromethane. The extract was driedover anhydrous magnesium and concentrated under reduced pressure. Thecrystal thus obtained was recrystallized from ethyl acetate to give2-[2-(4-chloro-2-methylphenoxymethyl)-α-hydroxybenzyl]-1-methylimidazole(0.57 g, 55.4%) as colorless crystals. mp. 159-160° C.

¹ H-NMR (CDCl₃) δ ppm: 2.19 (3H, s), 3.36 (3H, s), 4.98 (1H, d, J=12.2),5.26 (1H, d, J=12.2), 6.10 (1H, s), 6.77 (1H, d, J=7.9), 6.84 (1H, s),7.00 (1H, s), 7.07-7.54 (6H, m).

According to the same manner as that of the synthesis of theintermediate in Example 1 or 3, various compounds of the formula (IV) ofthis invention, which are intermediates for production of the compound(I), were synthesized. The compounds thus obtained and their physicaldata are shown in the following Tables 1-3. In the following tables thephysical data of the compounds obtained in Examples 1 and 3 are alsolisted.

                                      TABLE 1                                     __________________________________________________________________________      #STR17##                                                                       -                                                                          No  R.sup.1 R.sup.2                                                                              M  n  Physical data                                        __________________________________________________________________________    IV-1                                                                              3-Me-5- C.sub.6 H.sub.5                                                                      O  0  .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.23(3H,                                s), 2.99(1H, d,                                         isoxazolyl    J=6.1), 5.99(1H, s), 6.17(1H, d, J=6.7), 6.83-                      7.53(9H, m).                                                             IV-2 3-Me-5- 4-Ph-- O 1 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.25(3H,                               s), 3.08(1H, d,                                         isoxazolyl C.sub.6 H.sub.4   J=4.3), 5.08(1H, d, J=11.6), 5.19(1H, d,                                     J=11.0), 6.00(1H, s), 6.17(1H, d, J=4.3),                                     6.99(2H, d, J=8.5), 7.28-7.56(11H, m).                                   IV-3 3-Me-5- 3-CF.sub.3 -- O 1 .sup.1 H-NMR(CDCl                             .sub.3) δ ppm: 2.25(3H, s), 2.88(1H, d,                                   isoxazolyl C.sub.6 H.sub.4   J=4.3), 5.10(1H,                               d, J=11.0), 5.18(1H, d,                                     J=11.6), 5.96(1H, s), 6.15(1H, d, J=4.3), 7.06-                               7.56(8H, m).                                                             IV-4 3-Me-5- 2,5-Me.sub.2 -- O 1 .sup.1 H-NMR(CDCl.sub.3) δ ppm:                               2.14(3H, s), 2.26(3H,                                   isoxazolyl C.sub.6 H.sub.3   s), 2.32(3H, s), 3.10(1H, d, J=4.9),                                   5.01(1H, d,                                                 J=11.6), 5.13(1H, d, J=11.6), 6.01(1H, s),                                    6.16(1H, d, J=4.9), 6.71(1H, s), 6.72(1H, d,                                  J=7.9), 7.03(1H, d, J=7.9), 7.36-7.52(4H, m).                            IV-5 3-Me-5- 4-Cl-2-Me-- O 1 .sup.1 H-NMR(CDCl.sub.3) δ ppm:                                   2.15(3H, s), 2.25(3H,                                   isoxazolyl C.sub.6 H.sub.3   s), 2.94(1H, d, J=4.9), 5.04(1H, d,                                    J=11.6),                                                    5.11(1H, d, J=11.6), 5.96(1H, s), 6.15(1H, d,                                 J=4.9), 6.78(1H, d, J=8.6), 7.08-7.12(2H, m),                                 7.39-7.54(4H, m).                                                        IV-6 3-Et-5- 2,5-Me.sub.2 -- O 1 .sup.1 H-NMR(CDCl.sub.3) δ ppm:                               1.23(3H, t, J=7.3),                                     isoxazolyl C.sub.6 H.sub.3   2.13(3H, s), 2.32(3H, s), 2.65(2H, q,                                  J=7.3),                                                     3.16(1H, d, J=4.9), 5.01(1H, d, J=11.6),                                      5.12(1H, d, J=11.6), 6.04(1H, s), 6.16(1H, d,                                 J=4.9), 6.71(1H, s), 6.72(1H, d, J=7.9),                                      7.03(1H, d, J=7.9), 7.39-7.50(4H, m).                                    IV-7 3-Me-2- 2,5-Me.sub.2 -- O 1 .sup.1 H-NMR(CDCl.sub.3) δ ppm:                               1.87(3H, s), 2.16(3H,                                   isoxazolin-5-yl C.sub.6 H.sub.3   s), 2.34(3H, s), 2.79-2.88(3H, m),                                4.88-                                                       5.29(4H, m), 6.73(1H, d, J=7.9), 6.79(1H, s),                                 7.03(1H, d, J=7.3), 7.34-7.56(4H, m).                                  __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________    No R.sup.1 R.sup.2                                                                            M n Physical data                                             __________________________________________________________________________    IV-8                                                                             3-isoxazolyl                                                                          2,5-Me.sub.2 -                                                                     O 1 mp 86˜87° C.                                     C.sub.6 H.sub.3                                                             IV-9 3-isoxazolyl 4-Cl-2- O 1 mp 89˜91° C.                         Me-C.sub.6 H.sub.3                                                          IV-10 5-Me-3- 2-Me- O 1 .sup.1 H-NMR(CDCl.sub.3) δ ppm:2.23(3H,                           s),                                                          isoxazolyl C.sub.6 H.sub.4   2.37(3H, s), 2.97(1H, d, J=3.7), 5.11(1H,            d, J=11.6), 5.18(1H, d, J=11.8), 5.90(1H,                                     s), 6.20(1H, d, J=4.3), 6.87-6.91(2H, m),                                     7.13-7.18(2H, m), 7.34-7.55(4H, m).                                      IV-11 5-Me-3- 2,5-Me.sub.2 - O 1 .sup.1 H-NMR(CDCl.sub.3) δ                               ppm:2.18(3H, s),                                             isoxazolyl C.sub.6 H.sub.3   2.32(3H, s), 2.37(3H, s), 2.99(1H, d,                                   J=4.3), 5.09(1H, d, J=11.6), 5.17(1H, d,                                      J=11.6), 5.91(1H, s), 6.20(1H, d, J=4.3),                                     6.71(1H, d, J=7.3), 6.73(1H, s), 7.03(1H,                                     d, J=7.3), 7.36-7.54(4H, m).                          lV-12 3,5-Me.sub.2 - 2,5-Me.sub.2 - O 1 mp 188˜119° C.                               4-isoxazolyl C.sub.6 H.sub.3                              IV-13 4-Me-1,2,3- C.sub.6 H.sub.5 O 1 .sup.1 H-NMR(CDCl.sub.3) δ                          ppm:2.36(3H, s),                                             thiadiazol-5-yl    3.44(1H, d, J=3.7), 5.09(1H, d, J=10.4),                       5.20(1H, d, J=10.4), 6.39(1H, d, J=3.7),                                      6.92-6.95(2H, m), 7.03(1H, t, J=7.9), 7.20-                                   7.53(6H, m).                                                             IV-14 4-Me-1,2,3- 2,5-Me.sub.2 - O 1 mp 122˜123° C.                                  thiadiaxol-5-yl C.sub.6 H.sub.3                         __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________    No R.sup.1                                                                              R.sup.2                                                                             M       n Physical data                                       __________________________________________________________________________    IV-15                                                                            1-Me-2-                                                                              C.sub.6 H.sub.5                                                                     O       1 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 3.38(3H,                                s),                                                    imidazolyl    4.22(1H, brs), 4.99(1H, d, J=11.6),                                 5.34(1H, dd, J=11.6, 3.1), 6.14(1H, s),                                       6.84(1H, s), 6.92-7.03(3H, m), 7.15(1H,                                       d, J=4.9), 7.29-7.64(6H, m).                                             IV-16 1-Me-2- 2-Me- O 1 mp 130˜131° C.                            imidazolyl C.sub.6 H.sub.4                                                   IV-17 1-Me-2- 4-Cl-2-Me- O 1 mp 159˜160° C.                       imidazolyl C.sub.6 H.sub.3                                                   IV-18 1-Me-2 C.sub.6 H.sub.5 --ON═C(Me)-- 1 mp 104˜105°                               C.                                                    imidazolyl                                                                   IV-19 1-Me-2- 4-Cl-C.sub.6 H.sub.5 --ON═C(Me)-- 1                          imidazolyl                                                                   IV-20 1-Me-2- 2,5-Me.sub.2 - O 1                                               imidazolyl C.sub.6 H.sub.3                                                   IV-21 2-pyridyl 2,5-Me.sub.2 - O 1 .sup.1 H-NMR(CDCl.sub.3) δ                                   ppm:2.16(3H, s),                                        C.sub.6 H.sub.3   2.29(3H, s), 4.96(1H, d, J=11.6),                              5.32(1H, d, J=11.6), 5.33(1H, s),                                             6.05(1H, d, J=1.8), 6.64(1H, s),                                              6.67(1H, d, J=7.3), 7.00(1H, d, J=7.3),                                       7.16-7.64(7H, m), 8.57(1H, dd, J=4.9,                                         1.8).                                                                    IV-22 3-pyridyl 2,5-Me.sub.2 - O 1 .sup.1 H-NMR(CDCl.sub.3) δ                                   ppm:2.13(3H, s),                                        C.sub.6 H.sub.3   2.31(3H, s), 3.09(1H, brs), 5.00(1H, d,                        J=11.6), 5.07(1H, d, J=11.6), 6.19(1H,                                        s), 6.66(1H, s), 6.72(1H, d, J=7.3),                                          7.02(1H, d, J=7.3), 7.23-7.73(6H, m),                                         8.51(1H, dd, J=4.9, 1.8), 8.58(1H, d,                                         J=1.8).                                                                __________________________________________________________________________

Example 4

Synthesis of2-[2-(4-chloro-2-methylphenoxymethyl)-α-ethoxybenzyl]-1-methylimidazole(Compound No. I-449)

To a mixture of 0.34 g (0.9 mmol) of2-[2-(4-chloro-2-methylphenoxymethyl)-α-hydroxybenzyl]-1-methylimidazole,3 ml of N,N-dimethylformamide and 0.13 ml (1.8 mmol) of ethyl bromidewas added 0.05 g (1.3 mmol) of 60% sodium hydride under ice-cooling andstirred at the same temperature for 3 hours. After completion of thereaction, 100 ml of ether was added and washed twice with 80 ml ofbrine. The ether layer was dried over anhydrous magnesium andconcentrated under reduced pressure. The residue was purified by columnchromatography on silica gel (ethyl acetate/n-hexane) to give2-[2-(4-chloro-2-methylphenoxymethyl)-α-ethoxybenzyl]-1-methylimidazole(0.30 g, 89.9%) as colorless oil.

¹ H-NMR (CDCl₃) δ ppm: 1.26 (3H, t, J=7.3), 2.20 (3H, s), 3.46-3.64 (2H,m), 3.55 (3H, s), 4.95 (1H, d, J=12.8), 5.10 (1H, d, J=12.8), 5.84 (1H,s), 6-72(1H, d, J=8.6), 6.82 (1H, d, J=1.2), 6.94 (1H, d, J=1.2),7.04-7.54 (6H, m).

Example 5

Synthesis of5-[2-(1-ethoxyethyl)oxymethyl-α-methoxybenzyl]-3-methylisoxazole

To a mixture of 3.18 g (11 mmol) of 2-(1-ethoxyethyl)oxymethylphenyl3-methylisoxazol-5-yl ketone, 11 ml of tetrahydrofuran and 11 ml ofmethanol was added 0.42 g (11 mmol) of sodium borohydride underice-cooling and stirred at room temperature for an hour. Aftercompletion of the reaction, 300 ml of brine was added and extractedtwice with 100 ml of dichloromethane. The extract was dried overanhydrous magnesium and concentrated under reduced pressure to give 3.30g of a crude product of5-[2-(1-ethoxyethyl)oxymethyl-α-hydroxybenzyl]-3-methylisoxazole. To thecrude product, 22 ml of N,N-dimethylformamide and 1.03 ml (16.5 mmol) ofmethyl iodide was added and then 0.57 g (14.3 mmol) of 60% sodiumhydride was added under ice-cooling and stirred at the same temperaturefor an hour. After completion of the reaction, 200 ml of ether was addedand washed twice with 200 ml of brine. The ether layer was dried overanhydrous magnesium and concentrated under reduced pressure. The residuewas purified by column chromatography on silica gel (ethylacetate/n-hexane) to give5-[2-(1-ethoxyethyl)oxymethyl-α-methoxybenzyl]-3-methylisoxazole (3.18g, 94.7%) as colorless oil.

¹ H-NMR (CDCl₃) δ ppm: 1.21 (1.21) (3H, t, J=7.0), 1.31 (1.32) (3H, d),2.24 (3H, s), 3.47-3.67 (2H, m), 4.47-4.80 (3H, m), 5.72 (5.75) (1H, s),5.89 (1H, s), 7.30-7.55 (4H, m).

Example 6

Synthesis of 5-(2-hydroxymethyl-α-methoxybenzyl)-3-methylisoxazole(Compound No. X-1)

To 3.05 g (10 mmol) of5-[2-(1-ethoxyethyl)oxymethyl-α-methoxybenzyl]-3-methylisoxazole wasadded 0.25 g (1 mmol) of pyridinium p-toluenesulfonate and stirred underreflux for an hour. After completion of the reaction, 150 ml of brinewas added and extracted twice with 80 ml of dichloromethane. The extractwas dried over anhydrous magnesium and concentrated under reducedpressure to give 5-(2-hydroxymethyl-α-methoxybenzyl)-3-methylisoxazole(2.33 g, 99.9%) as colorless oil.

¹ H-NMR (CDCl₃) δ ppm: 2.12 (1H, brs), 2.27 (3H, s), 3.47 (3H, s), 4.70(2H, s), 5.70 (1H, s), 6.00 (1H, s), 7.34-7.44 (4H, m).

According to the same manner as that of the synthesis of theintermediate in Example 6, various compounds of the formula (X) of thisinvention, which are intermediates for production of the compound (I),were synthesized. The compounds thus obtained and their physical dataare shown in the following Table 4. In the following table the physicaldata of the compound (X-1) obtained in Example 6 are also listed.

                                      TABLE 4                                     __________________________________________________________________________      #STR18##                                                                       -                                                                          No   R.sup.1   R.sup.3                                                                          n  Physical data                                            __________________________________________________________________________    X-1  3-Me-5-isoxazolyl                                                                       Me 1  .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.12(1H, brs),                          2.27(3H,                                                       s), 3.47(3H, s), 4.70(2H, s), 5.70(1H, s), 6.00(1H,                           s), 7.34-7.44(4H, m).                                                     X-2 3-isoxazolyl Me 1 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.62(1H,                             dd, J=7.3, 5.5),                                               3.44(3H, s), 4.66-4.82(2H, m), 5.84(1H, s),                                   6.40(1H, d, J=1.8), 7.32-7.52(4H, m), 8.34(1H, d,                             J=1.8).                                                                   X-3 5-Me-3-isoxazolyl Me 1 .sup.1 H-NMR(CDCl.sub.3) δ ppm:                                 2.38(3H, d, J=1.2),                                            2.78(1H, t, J=7.3), 3.43(3H, s), 4.61-4.82(2H, m),                            5.73(1H, s), 6.02(1H, s), 7.31-7.53(4H, m).                               X-4 3-Me-5-isoxazolyl Me 0 .sup.1 H-NMR(CDCl.sub.3) δ ppm:                                 2.25(3H, s), 3.56(3H, s),                                      5.51(1H, s), 5.97(1H, s), 6.85-7.29(4H, m),                                   7.43(1H, s)                                                               X-5 5-Me-3-isoxazolyl Me 0                                                    X-6 3-isoxazolyl Me 0                                                         X-7 3-Me-5-isoxazolyl Et 0                                                    X-8 3-Me-5-isoxazolyl Et 1                                                    X-9 3,4-tetramethylene- Me 1 .sup.1 H-NMR(CDCl.sub.3) δ ppm:                               1.64-1.80(4H, m),                                           5-isoxazolyl   2.22(1H, t, J=6.1), 2.31-2.47(2H, m), 2.72(2H, t,                                     J=6.7), 3.45(3H, s), 4.62-4.74(2H, m), 5.73(1H,           s), 7.32-7.45(4H, m).                                                      X-10 4,5-tetramethylene- Me 1 .sup.1 H-NMR(CDCl.sub.3) δ ppm:                             1.64-1.86(4H, m), 2.25-                                     3-isoxazolyl   2.35(1H, m), 2.41-2.51(1H, m), 2.63-2.67(2H, m),                                      2.94(1H, t, J=7.3), 3.43(3H, s), 4.64-4.81(2H,                           m),                                                            5.77(1H, s), 7.29-7.51(4H, m).                                             X-11 2-isoxazolin-3-yl Me 1 .sup.1 H-NMR(CDCl.sub.3) δ ppm:                               2.37(1H, brs), 2.74-                                           3.10(2H, m), 3.42(3H, s), 4.21-4.37(2H, m), 4.68-                             4.81(2H, m), 5.53(1H, s), 7.31-7.53(4H, m).                             __________________________________________________________________________

Example 7

Synthesis of5-[2-(3-chloro-5-trifluoromethyl-2-pyridyloxymethyl)-α-methoxybenzyl]-3-methylisoxazole(Compound No. A-69)

To a mixture of 0.21 g (0.9 mmol) of5-(2-hydroxymethyl-α-methoxybenzyl)-3-methylisoxazole, 3 ml oftetrahydrofuran and 0.29 g (1.35 mmol) of2,3-dichloro-5-trifluoromethylpyridine was added 0.05 g (1.3 mmol) of60% sodium hydride under ice-cooling and stirred at room temperature for2 hours. After completion of the reaction, 100 ml of ether was added andwashed with 80 ml of brine. The ether layer was dried over anhydrousmagnesium and concentrated under reduced pressure. The residue waspurified by column chromatography on silica gel (ethyl acetate/n-hexane)to give5-[2-(3-chloro-5-trifluoromethyl-2-pyridyloxymethyl)-α-methoxybenzyl]-3-methylisoxazole(0.32 g, 86.1%) as colorless oil.

¹ H-NMR (CDCl₃) δ ppm: 2.24 (3H, s), 3.46 (3H, s), 5.57 (2H, s), 5.79(1H, s), 5.91 (1H, s), 7.35-7.56 (4H, m), 7.85 (1H, d, J=2.2), 8.33 (1H,t, J=1.2).

Example 8

Synthesis of 5-(2-chloromethyl-α-methoxybenzyl)-3-methylisoxazole(Compound No. XII-1)

To a mixture of 1.24 g (5.3 mmol) of5-(2-hydroxymethyl-α-methoxybenzyl)-3-methylisoxazole and 10 ml ofacetonitrile was added 1.67 g (6.36 mmol) of triphenylphosphine and 1.23ml (12.7 mmol) of carbon tetrachloride under ice-cooling and stirred atroom temperature overnight. After completion of the reaction, theresidue obtained by concentration under reduced pressure was purified bycolumn chromatography on silica gel (ethyl acetate/n-hexane) to give5-(2-chloromethyl-α-methoxybenzyl)-3-methylisoxazole (1.03 g, 77.2%) ascolorless oil.

¹ H-NMR (CDCl₃) δ ppm: 2.26 (3H, s), 3.46 (3H, s), 4.63 (1H, d, J=11.9),4.71 (1H, d, J=11.7), 5.75 (1H, s), 5.96 (1H, s), 7.32-7.53 (4H, m).

According to the same manner as that of the synthesis of theintermediate in Example 8, various compounds of the formula (XII) ofthis invention, which are intermediates for production of the compound(I), were synthesized. The compounds thus obtained and their physicaldata are shown in the following Table 5. In the following table thephysical data of the compound (XII-1) obtained in Example 8 are alsolisted.

                                      TABLE 5                                     __________________________________________________________________________      #STR19##                                                                       -                                                                          No  R.sup.1   R.sup.3                                                                          Y  Physical data                                             __________________________________________________________________________    XII-1                                                                             3-Me-5-isoxazolyl                                                                       Me Cl .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.26(3H, s),                            3.46(3H, s),                                                    4.63(1H, d, J=11.9), 4.71(1H, d, J=11.7), 5.75(1H, s),                        5.96(1H, s), 7.32-7.53(4H, m).                                            XII-2 3-isoxazolyl Me Cl .sup.1 H-NMR(CDCl.sub.3) δ ppm: 3.45(3H,                         s), 4.57(1H, d, J=11.6),                                        4.85(1H, d, J=11.6), 5.90(1H, s), 6.33(1H, d, J=1.2),                         7.29-7.62(4H, m), 8.33(1H, d, J=1.8).                                     XII-3 5-Me-3-isoxazolyl Me Cl .sup.1 H-NMR(CDCl.sub.3) δ ppm:                             2.37(3H, s), 3.43(3H, s),                                       4.56(1H, d, J=11.6), 4.85(1H, d, J=12.2), 5.93(1H, s),                        5.79(1H, s), 7.31-7.62(4H, m).                                            XII-4 3-Me-5-isoxazolyl Et Cl                                                 XII-5 3,4- Me Cl .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.60-1.79(4H,                            m), 2.05-                                                    tetramethylene-   2.48(2H, m), 2.71(2H, t, J=6.7), 3.45(3H, s),                                4.60(1H, d,                                                  5-isoxazolyl   J=11.6), 4.67(1H, d, J=11.6), 5.80(1H, s), 7.30-7.58(4H,                         m).                                                        XII-6 4,5- Me Cl .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.61-1.86(4H,                            m), 2.11-2.22(1H,                                            tetramethylene-   m), 2.38-2.48(1H, m), 2.61-2.66(2H, m), 3.45(3H, s),        3-isoxazolyl   4.56(1H, d, J=11.6), 4.89(1H, d, J=11.6), 5.83(1H, s),                               7.28-7.41(3H, m), 7.60-7.63(1H, m).                    XII-7 2-isoxazolin-3-yl Me Cl .sup.1 H-NMR(CDCl.sub.3) δ ppm:                             2.64-2.79(1H, m), 2.95-                                         3.09(1H, m), 3.43(3H, s), 4.20-4.37(2H, m), 4.53(1H, d,                       J=11.6), 4.87(1H, d, J=11.6), 5.60(1H, s), 7.30-7.59(4H, m).            __________________________________________________________________________

Example 9

Synthesis of5-[2-(2,5-dichlorophenoxymethyl)-α-methoxybenzyl]-3-methylisoxazole(Compound No. A-31)

To 0.25 g (1 mmol) of5-(2-chloromethyl-α-methoxybenzyl)-3-methylisoxazole, 2 ml ofN,N-dimethylformamide, 0.28 g (2 mmol) of potassium carbonate and 0.33 g(2 mmol) of 2,5-dichlorophenol were added and stirred at 80° C. for 3hours. After completion of the reaction, 100 ml of ether was added andwashed twice with 80 ml of brine. The ether layer was dried overanhydrous magnesium and concentrated under reduced pressure. The residuewas purified by column chromatography on silica gel (ethylacetate/n-hexane) and recrystallized from ether/n-hexane to give5-[2-(2,5-dichlorophenoxymethyl)-α-methoxybenzyl]-3-methylisoxazole(0.28 g, 74.0%) as colorless crystals. mp. 78.5-79.5° C.

¹ H-NMR (CDCl₃) δ ppm: 2.25 (3H, s), 3.46 (3H, s), 5.12 (1H, d, J=12.2),5.18 (1H, d, J=12.2), 5.70 (1H, s), 5.93 (1H, s), 6.89-6.95 (2H, m),7.28-7.55 (5H, m).

Example 10

Synthesis of 5-(2-formyl-α-methoxybenzyl)-3-methylisoxazole

To 50 ml of dichloromethane containing 2.44 ml (28 mmol) of oxalylchloride was added 2.13 ml (30 mmol) of dimethylsulfoxide dropwise below-55° C. over 3 minutes and thereafter stirred at -55 to -78° C. for 10minutes. Then, 20 ml of dichloromethane in which 2.33 g (10 ml) of5-(2-hydroxymethyl-α-methoxybenzyl)-3-methylisoxazole was dissolved wasadded dropwise below -60° C. over 8 minutes and thereafter stirred at-70 to -60° C. for 20 minutes. To the reaction solution, 7.0 ml (50mmol) of triethylamine was added dropwise below -60° C. over 10 minutesand stirred at -70 to -10° C. for an hour.

After completion of the reaction, 300 ml of an aqueous solution ofammonium chloride was added and extracted twice with 100 ml ofdichloromethane. The dichloromethane layer was dried over anhydrousmagnesium and concentrated under reduced pressure. The residue waspurified by column chromatography on silica gel (ethyl acetate/n-hexane)to give 5-(2-formyl-α-methoxybenzyl)-3-methylisoxazole (2.03 g, 87.8%)as oil.

¹ H-NMR (CDCl₃) δ ppm: 2.25 (3H, s), 3.47 (3H, s), 5.99 (1H, s), 6.37(1H, s), 7.55-7.87 (4H, m), 10.16 (1H, s).

Example 11

Synthesis of5-[α-methoxy-2-{4-(4-trifluoromethylphenyl)-2,3-diaza-1,3-pentadienyl}benzyl]-3-methylisoxazole(Compound No. A-393)

To 0.23 g (1 mmol) of 5-(2-formyl-α-methoxybenzyl)-3-methylisoxazole in2 ml of methanol was added 0.22 g (1.1 mmol) of4'-(trifluoromethyl)acetophenone hydrazone and stirred at roomtemperature for 3 hours. After completion of the reaction, methanol wasconcentrated under reduced pressure. The residue was purified by columnchromatography on silica gel (ethyl acetate/n-hexane) to give5-[α-methoxy-2-{4-(4-trifluoromethylphenyl)-2,3-diaza-1,3-pentadienyl}benzyl]-3-methylisoxazole(0.23 g, 55.4%) as oil.

¹ H-NMR (CDCl₃) δ ppm: 2.23 (3H, s), 2.44 (3H, s), 3.49 (3H, s), 5.81(1H, s), 6.26 (1H, s), 7.43-8.02 (8H, m), 8.67(1H, s).

Example 12

Synthesis of 5-(2-hydroxyiminomethyl-α-methoxybenzyl)-3-methylisoxazole

To 1.39 g (6 mmol) of 5-(2-formyl-α-methoxybenzyl)-3-methylisoxazole in12 ml of methanol was added 0.83 g (12 mmol) of hydroxylaminehydrochloride and 1.07 ml (13.2 mmol) of pyridine and stirred underreflux for 2 hours. After completion of the reaction, 200 ml of 0.1 Nhydrochloric acid was added and extracted twice with 100 ml ofdichloromethane. The dichloromethane layer was dried over anhydrousmagnesium and concentrated under reduced pressure. The residue waspurified by column chromatography on silica gel (ethyl acetate/n-hexane)to give 5-(2-hydroxyiminomethyl-α-methoxybenzyl)-3-methylisoxazole (1.20g, 81.2%) as oil.

¹ H-NMR (CDCl₃) δ ppm: 2.25 (3H, s), 3.44 (3H, s), 5.85 (2H, s),7.38-7.47 (2H, m), 7.52 (1H, s), 7.56-7.67 (2H, m), 8.41 (1H, 5).

Example 13

Synthesis of5-[α-methoxy-2-(4-phenyl-2-aza-3-oxa-1-pentenyl)benzyl]-3-methylisoxazole(Compound No. A-361)

To a mixture of 0.25 g (1 mmol) of5-(2-hydroxyiminomethyl-α-methoxybenzyl)-3-methylisoxazole, 3 ml ofN,N-dimethylformamide and 0.24 g (1.3 mmol) of α-methylbenzyl bromidewas added 0.05 g (1.3 mmol) of 60% sodium hydride under ice-cooling andstirred at the same temperature for 3 hours. After completion of thereaction, 100 ml of ether was added and washed twice with 80 ml ofbrine. The ether layer was dried over anhydrous magnesium andconcentrated under reduced pressure. The residue was purified by columnchromatography on silica gel (ethyl acetate/n-hexane) to give5-[α-methoxy-2-(4-phenyl-2-aza-3-oxa-1-pentenyl)benzyl]-3-methylisoxazole(0.32 g, 91.3%) as colorless oil.

¹ H-NMR (CDCl₃) δ ppm: 1.56 (1.61) (3H, d, J=6.7), 2.16 (2.23) (3H, s),3.27 (3.39) (3H, s), 5.26-5.35 (1H, m), 5.57 (5.69) (1H, s), 5.79 (5.91)(1H, s), 7.27-7.63 (9H, m), 8.30 (8.35) (1H, s).

Example 14

Synthesis of 2-(4-chloro-2-methylphenoxymethyl)phenyl-2-methoxyaceticacid hydrazide

To 1.05 g (3 mmol) of ethyl2-(4-chloro-2-methylphenoxymethyl)phenyl-2-methoxyacetate was added 6 mlof methanol and 0.75 g (15 mmol) of hydrazine monohydrate and stirred at60° C. for 16 hours. After completion of the reaction, 100 ml of brinewas added and extracted twice with 70 ml of dichloromethane. The extractwas dried over anhydrous magnesium and concentrated under reducedpressure to give2-(4-chloro-2-methylphenoxymethyl)phenyl-2-methoxyacetic acid hydrazide(0.93 g, 92.6%) as colorless oil.

¹ H-NMR (CDCl₃) δ ppm: 2.22 (3H, s), 3.35 (3H, s), 3.80 (2H, d, J=3.7),5.07 (1H, s), 5.08 (1H, d, J=11.6), 5.42 (1H, d, J=11.6), 6.86 (1H, d,J=9.2), 7.09-7.13 (2H, m), 7.33-7.51 (4H, m), 7.87 (1H, brs).

Example 15

Synthesis of2-[2-(4-chloro-2-methylphenoxymethyl)-α-methoxybenzyl]-1,3,4-oxadiazole(Compound No. L-41)

To 0.50 g (1.5 mmol) of2-(4-chloro-2-methylphenoxymethyl)phenyl-2-methoxyacetic acid hydrazidewas added 1.5 ml of ethyl orthoformate, stirred under reflux for 3hours, and thereafter concentrated under reduced pressure. To theresidue thus obtained, 4.5 ml of benzene and 0.03 g (0.15 mmol) ofp-toluenesulfonic acid monohydrate were added and stirred under refluxfor an hour. After completion of the reaction, 100 ml of water was addedand extracted twice with 50 ml of dichloromethane. The dichloromethanelayer was dried over anhydrous magnesium and concentrated under reducedpressure. The residue was purified by column chromatography on silicagel (ethyl acetate/n-hexane) to give2-[2-(4-chloro-2-methylphenoxymethyl)-α-methoxybenzyl]-1,3,4-oxadiazole(0.07 g, 13.5%) as colorless crystals. mp. 68-70° C.

¹ H-NMR (CDCl₃) δ ppm: 2.17 (3H, s), 3.47 (3H, s), 5.05 (1H, d, J=12.2),5.19 (1H, d, J=12.2), 5.94 (1H, s), 6.83 (1H, dd, J=7.3, 1.8), 7.10-7.13(2H, m), 7.40-7.71 (4H, m), 8.36 (1H, s).

Examples of the compounds represented by the formula (I) obtainable bythe same manner as that in Examples described above are the followingcompound groups A to O. Examples of combination of the substituents R²,R³, R⁴, M, and n of the compound groups A to O are shown in Tables 6 to30. The physical data of the compounds are shown in Tables 31 to 41. Thephysical data of the compounds obtained in the above Examples are alsolisted. "No." represents a compound number. ##STR20##

                  TABLE 6                                                         ______________________________________                                        No    R.sup.2        R.sup.3                                                                             R.sup.4 M   n                                      ______________________________________                                        1     C.sub.6 H.sub.5                                                                              Me    H       O   1                                        2 2-F--C.sub.6 H.sub.4 Me H O 1                                               3 3-F--C.sub.6 H.sub.4 Me H O 1                                               4 4-F--C.sub.6 H.sub.4 Me H O 1                                               5 2-Cl--C.sub.6 H.sub.4 Me H O 1                                              6 3-Cl--C.sub.6 H.sub.4 Me H O 1                                              7 4-Cl--C.sub.6 H.sub.4 Me H O 1                                              8 2-Br--C.sub.6 H.sub.4 Me H O 1                                              9 3-Br--C.sub.6 H.sub.4 Me H O 1                                              10 4-Br--C.sub.6 H.sub.4 Me H O 1                                             11 3-I--C.sub.6 H.sub.4 Me H O 1                                              12 2-Me--C.sub.6 H.sub.4 Me H O 1                                             13 3-Me--C.sub.6 H.sub.4 Me H O 1                                             14 4-Me--C.sub.6 H.sub.4 Me H O 1                                             15 2-Et--C.sub.6 H.sub.4 Me H O 1                                             16 3-Et--C.sub.6 H.sub.4 Me H O 1                                             17 4-Et--C.sub.6 H.sub.4 Me H O 1                                             18 2-MeO--C.sub.6 H.sub.4 Me H O 1                                            19 3-MeO--C.sub.6 H.sub.4 Me H O 1                                            20 4-MeO--C.sub.6 H.sub.4 Me H O 1                                          ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                        No    R.sup.2          R.sup.3                                                                             R.sup.4                                                                              M   n                                     ______________________________________                                        21    2-CF.sub.3 --C.sub.6 H.sub.4                                                                   Me    H      O   1                                       22 3-CF.sub.3 --C.sub.6 H.sub.4 Me H O 1                                      23 4-CF.sub.3 --C.sub.6 H.sub.4 Me H O 1                                      24 2,4-F.sub.2 --C.sub.6 H.sub.3 Me H O 1                                     25 2,5-F.sub.2 --C.sub.6 H.sub.3 Me H O 1                                     26 2,6-F.sub.2 --C.sub.6 H.sub.3 Me H O 1                                     27 3,4-F.sub.2 --C.sub.6 H.sub.3 Me H O 1                                     28 3,5-F.sub.2 --C.sub.6 H.sub.3 Me H O 1                                     29 2,3-Cl.sub.2 --C.sub.6 H.sub.3 Me H O 1                                    30 2,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H O 1                                    31 2,5-Cl.sub.2 --C.sub.6 H.sub.3 Me H O 1                                    32 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H O 1                                    33 3,5-Cl.sub.2 --C.sub.6 H.sub.3 Me H O 1                                    34 2,3-Me.sub.2 --C.sub.6 H.sub.3 Me H O 1                                    35 2,4-Me.sub.2 --C.sub.6 H.sub.3 Me H O 1                                    36 2,5-Me.sub.2 --C.sub.6 H.sub.3 Me H O 1                                    37 3,4-Me.sub.2 --C.sub.6 H.sub.3 Me H O 1                                    38 3,5-Me.sub.2 --C.sub.6 H.sub.3 Me H O 1                                    39 2-Cl-4-Me--C.sub.6 H.sub.3 Me H O 1                                        40 2-Cl-5-Me--C.sub.6 H.sub.3 Me H O 1                                      ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                        No    R.sup.2          R.sup.3                                                                             R.sup.4                                                                              M   n                                     ______________________________________                                        41    4-Cl-2-Me--C.sub.6 H.sub.3                                                                     Me    H      O   1                                       42 4-Cl-3-Me--C.sub.6 H.sub.3 Me H O 1                                        43 3-Ph--C.sub.6 H.sub.4 Me H O 1                                             44 4-Ph--C.sub.6 H.sub.4 Me H O 1                                             45 3-i-PrO--C.sub.6 H.sub.4 Me H O 1                                          46 3-i-Pr--C.sub.6 H.sub.4 Me H O 1                                           47 4-i-Pr--C.sub.6 H.sub.4 Me H O 1                                           48 3-t-Bu--C.sub.6 H.sub.4 Me H O 1                                           49 2-MeS--C.sub.6 H.sub.4 Me H O 1                                            50 4-MeS--C.sub.6 H.sub.4 Me H O 1                                            51 2,3,6-F.sub.3 --C.sub.6 H.sub.2 Me H O 1                                   52 2,4,5-Cl.sub.3 --C.sub.6 H.sub.2 Me H O 1                                  53 4-PhO--C.sub.6 H.sub.4 Me H O 1                                            54 3,4,5-(MeO).sub.3 --C.sub.6 H.sub.2 Me H O 1                               55 2,3,5-Me.sub.3 --C.sub.6 H.sub.2 Me H O 1                                  56 3,4,5-Me.sub.3 --C.sub.6 H.sub.2 Me H O 1                                  57 C.sub.6 F.sub.5 Me H O 1                                                   58 4-Cl-3-Et--C.sub.6 H.sub.3 Me H O 1                                        59 3-EtO--C.sub.6 H.sub.4 Me H O 1                                            60 4-EtO--C.sub.6 H.sub.4 Me H O 1                                          ______________________________________                                    

                  TABLE 9                                                         ______________________________________                                        No    R.sup.2            R.sup.3                                                                             R.sup.4                                                                             M   n                                    ______________________________________                                        61    2-pryidyl          Me    H     O   1                                      62 5-Cl-2-pyridyl Me H O 1                                                    63 3-Cl-2-pyridyl Me H O 1                                                    64 6-Cl-2-pyridyl Me H O 1                                                    65 3,5-Cl.sub.2 -2-pyridyl Me H O 1                                           66 5-CF.sub.3 -2-pyridyl Me H O 1                                             67 3-CF.sub.3 -2-pyridyl Me H O 1                                             68 3-CF.sub.3 -5-Cl-2-pyridyl Me H O 1                                        69 5-CF.sub.3 -3-Cl-2-pyridyl Me H O 1                                        70 2-benzothiazolyl Me H O 1                                                  71 2-benzoxazolyl Me H O 1                                                    72 2-quinolyl Me H O 1                                                        73 5-CF.sub.3 -1,3,4-thiadiazol-2-yl Me H O 1                                 74 2-pyrimidyl Me H O 1                                                       75 6-Cl-4-pyrimidyl Me H O 1                                                  76 6-Cl-2-benzothiazolyl Me H O 1                                             77 6-Cl-2-pyrazinyl Me H O 1                                                  78 3,6-Me.sub.2 -2-pyrazinyl Me H O 1                                         79 3-Ph-5-isoxazolyl Me H O 1                                                 80 5-Me-3-isoxazolyl Me H O 1                                               ______________________________________                                    

                  TABLE 10                                                        ______________________________________                                        No   R.sup.2       R.sup.3                                                                             R.sup.4                                                                             M         n                                    ______________________________________                                        81   C.sub.6 H.sub.5                                                                             Me    H     --ON═C(Me)--                                                                        1                                      82 2-F--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                               83 3-F--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                               84 4-F--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                               85 2-Cl--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                              86 3-Cl--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                              87 4-Cl--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                              88 2-Br--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                              89 3-Br--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                              90 4-Br--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                              91 3-I--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                               92 2-Me--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                              93 3-Me--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                              94 4-Me--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                              95 2-Et--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                              96 3-Et--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                              97 4-Et--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                              98 2-MeO--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                             99 3-MeO--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                             100  4-MeO--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                         ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                        No   R.sup.2       R.sup.3                                                                             R.sup.4                                                                             M         n                                    ______________________________________                                        101  2-CF.sub.3 --C.sub.6 H.sub.4                                                                Me    H     --ON═C(Me)--                                                                        1                                      102 3-CF.sub.3 --C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                      103 4-CF.sub.3 --C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                      104 2,4-F.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Me)-- 1                     105 2,5-F.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Me)-- 1                     106 3,5-F.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Me)-- 1                     107 2,3-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Me)-- 1                    108 2,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Me)-- 1                    109 2,5-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Me)-- 1                    110 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Me)-- 1                    111 3,5-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Me)-- 1                    112 2,3-Me.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Me)-- 1                    113 2,4-Me.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Me)-- 1                    114 2,5-Me.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Me)-- 1                    115 3,4-Me.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Me)-- 1                    116 3,5-Me.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Me)-- 1                    117 3-Cl-4-Me--C.sub.6 H.sub.3 Me H --ON═C(Me)-- 1                        118 3-Cl-5-Me--C.sub.6 H.sub.3 Me H --ON═C(Me)-- 1                        119 4-Cl-3-Me--C.sub.6 H.sub.3 Me H --ON═C(Me)-- 1                        120 3,4,5-Me.sub.3 --C.sub.6 H.sub.2 Me H --ON═C(Me)-- 1                ______________________________________                                    

                  TABLE 12                                                        ______________________________________                                        No   R.sup.2        R.sup.3                                                                             R.sup.4                                                                             M         n                                   ______________________________________                                        121  3-Ph--C.sub.6 H.sub.4                                                                        Me    H     --ON═C(Me)--                                                                        1                                     122 4-Ph--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                             123 4-PhO--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                            124 3-i-PrO--C.sub.6 H.sub.4 Me H --ON═C(Me)-- 1                          125 2-pyridyl Me H --ON═C(Me)-- 1                                         126 3-pyridyl Me H --ON═C(Me)-- 1                                         127 4-pyridyl Me H --ON═C(Me)-- 1                                         125 2-furyl Me H --ON═C(Me)-- 1                                           129 3-furyl Me H --ON═C(Me)-- 1                                           130 2-thienyl Me H --ON═C(Me)-- 1                                         131 3-thienyl Me H --ON═C(Me)-- 1                                         132 2-naphthyl Me H --ON═C(Me)-- 1                                        133 3-naphthyl Me H --ON═C(Me)-- 1                                        134 2-thiazolyl Me H --ON═C(Me)-- 1                                       135 2-pyrazinyl Me H --ON═C(Me)-- 1                                       136 5-Me-2-furyl Me H --ON═C(Me)-- 1                                      137 5-Cl-2-thienyl Me H --ON═C(Me)-- 1                                    138 5-Br-2-thienyl Me H --ON═C(Me)-- 1                                    139 3-Ph-5-isoxazolyl Me H --ON═C(Me)-- 1                                 140 5-Me-3-isoxazolyl Me H --ON═C(Me)-- 1                               ______________________________________                                    

                  TABLE 13                                                        ______________________________________                                        No   R.sup.2      R.sup.3                                                                             R.sup.4                                                                             M          n                                    ______________________________________                                        141  C.sub.6 H.sub.5                                                                            Me    H     --ON═C(SMe)--                                                                        1                                      142 2-F--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                             143 3-F--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                             144 4-F--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                             145 2-Cl--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                            146 3-Cl--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                            147 4-Cl--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                            148 2-Br--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                            149 3-Br--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                            150 4-Br--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                            151 3-I--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                             152 2-Me--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                            153 3-Me--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                            154 4-Me--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                            155 2-Et--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                            156 3-Et--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                            157 4-Et--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                            158 2-MeO--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                           159 3-MeO--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                           160 4-MeO--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                         ______________________________________                                    

                  TABLE 14                                                        ______________________________________                                        No   R.sub.2       R.sub.3                                                                             R.sub.4                                                                             M          n                                   ______________________________________                                        161  2-CF.sub.3 --C.sub.6 H.sub.4                                                                Me    H     --ON═C(SMe)--                                                                        1                                     162 3-CF.sub.3 --C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                     163 4-CF.sub.3 --C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                     164 2,4-F.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SMe)-- 1                    165 2,5-F.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SMe)-- 1                    166 3,5-F.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SMe)-- 1                    167 2,3-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SMe)-- 1                   168 2,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SMe)-- 1                   169 2,5-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SMe)-- 1                   170 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SMe)-- 1                   171 3,5-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SMe)-- 1                   172 2,3-Me.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SMe)-- 1                   173 2,4-Me.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SMe)-- 1                   174 2,5-Me.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SMe)-- 1                   175 3,4-Me.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SMe)-- 1                   176 3,5-Me.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SMe)-- 1                   177 3-Cl-4-Me--C.sub.6 H.sub.3 Me H --ON═C(SMe)-- 1                       178 3-Cl-5-Me--C.sub.6 H.sub.3 Me H --ON═C(SMe)-- 1                       179 4-Cl-3-Me--C.sub.6 H.sub.3 Me H --ON═C(SMe)-- 1                       180 3,4,5-Me.sub.3 --C.sub.6 H.sub.2 Me H --ON═C(SMe)-- 1               ______________________________________                                    

                  TABLE 15                                                        ______________________________________                                        No    R.sup.2      R.sup.3                                                                              R.sup.4                                                                            M          n                                   ______________________________________                                        181   3-Ph--C.sub.6 H.sub.4                                                                      Me     H    --ON═C(SMe)--                                                                        1                                     182 4-Ph--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                            183 4-PhO--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                           184 3-i-PrO--C.sub.6 H.sub.4 Me H --ON═C(SMe)-- 1                         185 2-pyridyl Me H --ON═C(SMe)-- 1                                        186 3-pyridyl Me H --ON═C(SMe)-- 1                                        187 4-pyridyl Me H --ON═C(SMe)-- 1                                        188 2-furyl Me H --ON═C(SMe)-- 1                                          189 3-furyl Me H --ON═C(SMe)-- 1                                          190 2-thienyl Me H --ON═C(SMe)-- 1                                        191 3-thienyl Me H --ON═C(SMe)-- 1                                        192 2-naphthyl Me H --ON═C(SMe)-- 1                                       193 3-naphthyl Me H --ON═C(SMe)-- 1                                       194 2-thiazolyl Me H --ON═C(SMe)-- 1                                      195 2-pyrazinyl Me H --ON═C(SMe)-- 1                                      196 5-Me-2-furyl Me H --ON═C(SMe)-- 1                                     197 5-Cl-2-thienyl Me H --ON═C(SMe)-- 1                                   198 5-Br-2-thienyl Me H --ON═C(SMe)-- 1                                   199 3-Ph-5-isoxazolyl Me H --ON═C(SMe)-- 1                                200 5-Me-3-isoxazolyl Me H --ON═C(SMe)-- 1                              ______________________________________                                    

                  TABLE 16                                                        ______________________________________                                        No   R.sup.2        R.sup.3                                                                             R.sup.4                                                                             M         n                                   ______________________________________                                        201  C.sub.6 H.sub.5                                                                              Me    H     --ON═C(Et)--                                                                        1                                     202 4-F--C.sub.6 H.sub.4 Me H --ON═C(Et)-- 1                              203 3-F--C.sub.6 H.sub.4 Me H --ON═C(Et)-- 1                              204 3-Cl--C.sub.6 H.sub.4 Me H --ON═C(Et)-- 1                             205 4-Cl--C.sub.6 H.sub.4 Me H --ON═C(Et)-- 1                             206 4-Br--C.sub.6 H.sub.4 Me H --ON═C(Et)-- 1                             207 3-Me--C.sub.6 H.sub.4 Me H --ON═C(Et)-- 1                             208 4-Me--C.sub.6 H.sub.4 Me H --ON═C(Et)-- 1                             209 4-Et--C.sub.6 H.sub.4 Me H --ON═C(Et)-- 1                             210 3-MeO--C.sub.6 H.sub.4 Me H --ON═C(Et)-- 1                            211 4-MeO--C.sub.6 H.sub.4 Me H --ON═C(Et)-- 1                            212 3-CF.sub.3 --C.sub.6 H.sub.4 Me H --ON═C(Et)-- 1                      213 4-CF.sub.3 --C.sub.6 H.sub.4 Me H --ON═C(Et)-- 1                      214 3,4-F.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Et)-- 1                     215 3,5-F.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Et)-- 1                     216 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Et)-- 1                    217 3,5-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Et)-- 1                    218 3,4-Me.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(Et)-- 1                    219 4-Cl-3-Me--C.sub.6 H.sub.3 Me H --ON═C(Et)-- 1                        220 3-Ph--C.sub.6 H.sub.4 Me H --ON═C(Et)-- 1                           ______________________________________                                    

                  TABLE 17                                                        ______________________________________                                        No   R.sup.2        R.sup.3                                                                             R.sup.4                                                                             M         n                                   ______________________________________                                        221  C.sub.6 H.sub.5                                                                              Me    H     --ON═C(SEt)--                                                                       1                                     222 4-F--C.sub.6 H.sub.4 Me H --ON═C(SEt)-- 1                             223 3-F--C.sub.6 H.sub.4 Me H --ON═C(SEt)-- 1                             224 3-Cl--C.sub.6 H.sub.4 Me H --ON═C(SEt)-- 1                            225 4-Cl--C.sub.6 H.sub.4 Me H --ON═C(SEt)-- 1                            226 4-Br--C.sub.6 H.sub.4 Me H --ON═C(SEt)-- 1                            227 3-Me--C.sub.6 H.sub.4 Me H --ON═C(SEt)-- 1                            228 4-Me--C.sub.6 H.sub.4 Me H --ON═C(SEt)-- 1                            229 4-Et--C.sub.6 H.sub.4 Me H --ON═C(SEt)-- 1                            230 3-MeO--C.sub.6 H.sub.4 Me H --ON═C(SEt)-- 1                           231 4-MeO--C.sub.6 H.sub.4 Me H --ON═C(SEt)-- 1                           232 3-CF.sub.3 --C.sub.6 H.sub.4 Me H --ON═C(SEt)-- 1                     233 4-CF.sub.3 --C.sub.6 H.sub.4 Me H --ON═C(SEt)-- 1                     234 3,4-F.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SEt)-- 1                    235 3,5-F.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SEt)-- 1                    236 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SEt)-- 1                   237 3,5-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SEt)-- 1                   238 3,4-Me.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(SEt)-- 1                   239 4-Cl-3-Me--C.sub.6 H.sub.3 Me H --ON═C(SEt)-- 1                       240 3-Ph--C.sub.6 H.sub.4 Me H --ON═C(SEt)-- 1                          ______________________________________                                    

                  TABLE 18                                                        ______________________________________                                        No   R.sup.2       R.sup.3     R.sup.4                                                                             M   n                                    ______________________________________                                        241  C.sub.6 H.sub.5     Me    H     O   0                                      242 4-F--C.sub.6 H.sub.4 Me H O 0                                             243 3-F--C.sub.6 H.sub.4 Me H O 0                                             244 3-Cl--C.sub.6 H.sub.4 Me H O 0                                            245 4-Cl--C.sub.6 H.sub.4 Me H O 0                                            246 4-Br--C.sub.6 H.sub.4 Me H O 0                                            247 3-Me--C.sub.6 H.sub.4 Me H O 0                                            248 4-Me--C.sub.6 H.sub.4 Me H O 0                                            249 3-CF.sub.3 --C.sub.6 H.sub.4 Me H O 0                                     250 4-CF.sub.3 --C.sub.6 H.sub.4 Me H O 0                                     251 3,4-F.sub.2 --C.sub.6 H.sub.3 Me H O 0                                    252 3,5-F.sub.2 --C.sub.6 H.sub.3 Me H O 0                                    253 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H O 0                                   254 3,5-Cl.sub.2 --C.sub.6 H.sub.3 Me H O 0                                   255 3,4-Me.sub.2 --C.sub.6 H.sub.3 Me H O 0                                   256 4-Cl-3-Me--C.sub.6 H.sub.3 Me H O 0                                       257 5-CF.sub.3 -2-pyridyl Me H O 0                                            258 5-CF.sub.3 -3-Cl2-2-pyridyl Me H O 0                                      259 3,5-Cl.sub.2 -2-pyridyl Me H O 0                                          260 6-(2-CN--C6H4O)-4-pyrimidyl Me H O 0                                    ______________________________________                                    

                  TABLE 19                                                        ______________________________________                                        No   R.sup.2      R.sup.3                                                                              R.sup.4                                                                            M           n                                   ______________________________________                                        261  C.sub.6 H.sub.5                                                                            Me     H    --N(Ac)N═C(Me)--                                                                      1                                     262 4-F--C.sub.6 H.sub.4 Me H --N(Ac)N═C(Me)-- 1                          263 3-F--C.sub.6 H.sub.4 Me H --N(Ac)N═C(Me)-- 1                          264 3-Cl--C.sub.6 H.sub.4 Me H --N(Ac)N═C(Me)-- 1                         265 4-Cl--C.sub.6 H.sub.4 Me H --N(Ac)N═C(Me)-- 1                         266 4-Br--C.sub.6 H.sub.4 Me H --N(Ac)N═C(Me)-- 1                         267 3-Me--C.sub.6 H.sub.4 Me H --N(Ac)N═C(Me)-- 1                         268 4-Me--C.sub.6 H.sub.4 Me H --N(Ac)N═C(Me)-- 1                         269 4-Et--C.sub.6 H.sub.4 Me H --N(Ac)N═C(Me)-- 1                         270 3-MeO--C.sub.6 H.sub.4 Me H --N(Ac)N═C(Me)-- 1                        271 4-MeO--C.sub.6 H.sub.4 Me H --N(Ac)N═C(Me)-- 1                        272 3-CF.sub.3 --C.sub.6 H.sub.4 Me H --N(Ac)N═C(Me)-- 1                  273 4-CF.sub.3 --C.sub.6 H.sub.4 Me H --N(Ac)N═C(Me)-- 1                  274 3,4-F.sub.2 --C.sub.6 H.sub.3 Me H --N(Ac)N═C(Me)-- 1                 275 3,5-F.sub.2 --C.sub.6 H.sub.3 Me H --N(Ac)N═C(Me)-- 1                 276 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H --N(Ac)N═C(Me)-- 1                277 3,5-Cl.sub.2 --C.sub.6 H.sub.3 Me H --N(Ac)N═C(ME)-- 1                278 3,4-Me.sub.2 --C.sub.6 H.sub.3 Me H --N(Ac)N═C(Me)-- 1                279 4-Cl-3-Me--C.sub.6 H.sub.3 Me H --N(Ac)N═C(Me)-- 1                    280 3-Ph--C.sub.6 H.sub.4 Me H --N(Ac)N═C(Me)-- 1                         281 C.sub.6 H.sub.5 Me H --ON═C(CN)-- 1                                 ______________________________________                                    

                  TABLE 20                                                        ______________________________________                                        No   R.sup.2        R.sup.3                                                                             R.sup.4                                                                             M         n                                   ______________________________________                                        282  4-F--C.sub.6 H.sub.4                                                                         Me    H     --ON═C(CN)--                                                                        1                                     283 3-F--C.sub.6 H.sub.4 Me H --ON═C(CN)-- 1                              284 3-Cl--C.sub.6 H.sub.4 Me H --ON═C(CN)-- 1                             285 4-Cl--C.sub.6 H.sub.4 Me H --ON═C(CN)-- 1                             286 4-Br--C.sub.6 H.sub.4 Me H --ON═C(CN)-- 1                             287 3-Me--C.sub.6 H.sub.4 Me H --ON═C(CN)-- 1                             288 4-Me--C.sub.6 H.sub.4 Me H --ON═C(CN)-- 1                             289 4-Et--C.sub.6 H.sub.4 Me H --ON═C(CN)-- 1                             290 3-MeO--C.sub.6 H.sub.4 Me H --ON═C(CN)-- 1                            291 4-MeO--C.sub.6 H.sub.4 Me H --ON═C(CN)-- 1                            292 3-CF.sub.3 --C.sub.6 H.sub.4 Me H --ON═C(CN)-- 1                      293 4-CF.sub.3 --C.sub.6 H.sub.4 Me H --ON═C(CN)-- 1                      294 3,4-F.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(CN)-- 1                     295 3,5-F.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(CN)-- 1                     296 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(CN)-- 1                    297 3,5-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(CN)-- 1                    298 3,4-Me.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(CN)-- 1                    299 4-Cl-3-Me--C.sub.6 H.sub.3 Me H --ON═C(CN)-- 1                        300 3-Ph--C.sub.6 H.sub.4 Me H --ON═C(CN)-- 1                             301 C.sub.6 H.sub.5 Me H --ON═C(CF.sub.3)-- 1                             302 4-F--C.sub.6 H.sub.4 Me H --ON═C(CF.sub.3)-- 1                      ______________________________________                                    

                  TABLE 21                                                        ______________________________________                                        No    R.sup.2       R.sup.3                                                                             R.sup.4                                                                             M         n                                   ______________________________________                                        303   3-F--C.sub.6 H.sub.4                                                                        Me    H     --ON═C(CF.sub.3)--                                                                  1                                     304 3-Cl--C.sub.6 H.sub.4 Me H --ON═C(CF.sub.3)-- 1                       305 4-Cl--C.sub.6 H.sub.4 Me H --ON═C(CF.sub.3)-- 1                       306 4-Br--C.sub.6 H.sub.4 Me H --ON═C(CF.sub.3)-- 1                       307 3-Me--C.sub.6 H.sub.4 Me H --ON═C(CF.sub.3)-- 1                       308 4-Me--C.sub.6 H.sub.4 Me H --ON═C(CF.sub.3)-- 1                       309 4-Et--C.sub.6 H.sub.4 Me H --ON═C(CF.sub.3)-- 1                       310 3-MeO--C.sub.6 H.sub.4 Me H --ON═C(CF.sub.3)-- 1                      311 4-MeO--C.sub.6 H.sub.4 Me H --ON═C(CF.sub.3)-- 1                      312 3-CF.sub.3 --C.sub.6 H.sub.4 Me H --ON═C(CF.sub.3)-- 1                313 4-CF.sub.3 --C.sub.6 H.sub.4 Me H --ON═C(CF.sub.3)-- 1                314 3,4-F.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(CF.sub.3)-- 1                                                        315 3,5-F.sub.2 --C.sub.6                                                    H.sub.3 Me H --ON═C(CF.sub.3                                              )-- 1                                 316 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═C(CF.sub.3)-- 1                                                       317 3,5-Cl.sub.2 --C.sub.6                                                   H.sub.3 Me H --ON═C(CF.sub.3                                              )-- 1                                 318 3,4-Me2--C.sub.6 H.sub.3 Me H --ON═C(CF.sub.3)-- 1                    319 4-Cl--3-Me-C.sub.6 H.sub.3 Me H --ON═C(CF.sub.3)-- 1                  320 3-Ph--C.sub.6 H.sub.4 Me H --ON═C(CF.sub.3)-- 1                       321 morpholino Me H --ON═C(Me)- 1                                         322 2-Me-morpholino Me H --ON═C(Me)- 1                                    323 2,6-Me.sub.2 -morpholino Me H --ON═C(Me)- 1                         ______________________________________                                    

                  TABLE 22                                                        ______________________________________                                        No    R.sup.2       R.sup.3                                                                             R.sup.4                                                                             M         n                                   ______________________________________                                        324   3,5-Me.sub.2 -morpholino                                                                    Me    H     --ON═C(Me)-                                                                         1                                     325 piperidino Me H --ON═C(Me)- 1                                         326 3-Me-piperidino Me H --ON═C(Me)- 1                                    327 3,5-Me.sub.2 -piperidino Me H --ON═C(Me)- 1                           328 4-Me-piperazino Me H --ON═C(Me)- 1                                    329 pyrrolidino Me H --ON═C(Me)- 1                                        330 homopiperidino Me H --ON═C(Me)- 1                                     331 morpholino Me H --ON═C(Et)- 1                                         332 2-Me-morpholino Me H --ON═C(Et)- 1                                    333 2,6-Me.sub.2 -morpholino Me H --ON═C(Et)- 1                           334 3,5-Me.sub.2 -morpholino Me H --ON═C(Et)- 1                           335 piperidino Me H --ON═C(Et)- 1                                         336 3-Me-piperidino Me H --ON═C(Et)- 1                                    337 3,5-Me.sub.2 -piperidino Me H --ON═C(Et)- 1                           338 4-Me-piperazino Me H --ON═C(Et)- 1                                    339 pyrrolidino Me H --ON═C(Et)- 1                                        340 homopiperidino Me H --ON═C(Et)- 1                                     341 morpholino Me H --ON═C(CF.sub.3)-- 1                                  342 2-Me-morpholino Me H --ON═C(CF.sub.3)-- 1                             343 2,6-Me.sub.2 -morpholino Me H --ON═C(CF.sub.3)-- 1                    344 3,5-Me.sub.2 -morpholino Me H --ON═C(CF.sub.3)-- 1                  ______________________________________                                    

                  TABLE 23                                                        ______________________________________                                        No    R.sup.2      R.sup.3                                                                             R.sup.4                                                                           M            n                                   ______________________________________                                        345   piperidino   Me    H   --ON═C(CF.sub.3)--                                                                     1                                     346 3-Me-piperidino Me H --ON═C(CF.sub.3)-- 1                             347 3,5-Me.sub.2 -piperidino Me H --ON═C(CF.sub.3)-- 1                    348 4-Me-piperazino Me H --ON═C(CF.sub.3)-- 1                             349 pyrrolidino Me H --ON═C(CF.sub.3)-- 1                                 350 homopiperidino Me H --ON═C(CF.sub.3)-- 1                              351 morpholino Me H --ON═C(CN)-- 1                                        352 2-Me-morpholino Me H --ON═C(CN)-- 1                                   353 2,6-Me.sub.2 -morpholino Me H --ON═C(CN)-- 1                          354 3,5-Me.sub.2 -morpholino Me H --ON═C(CN)-- 1                          355 pipendino Me H --ON═C(CN)-- 1                                         356 3-Me-piperidino Me H --ON═C(CN)-- 1                                   357 3,5-Me.sub.2 -piperidino Me H --ON═C(CN)-- 1                          358 4-Me-piperazino Me H --ON═C(CN)-- 1                                   359 pyrrolidino Me H --ON═C(CN)-- 1                                       360 homopiperidino Me H --ON═C(CN)-- 1                                    361 C.sub.6 H.sub.5 Me H --CH═NOCH(CH.sub.3)-- 0                          362 4-F--C.sub.6 H.sub.4 Me H --CH═NOCH(CH.sub.3)-- 0                     363 3-F--C.sub.6 H.sub.4 Me H --CH═NOCH(CH.sub.3)-- 0                     364 3-Cl--C.sub.6 H.sub.4 Me H --CH═NOCH(CH.sub.3)-- 0                    365 4-Cl--C.sub.6 H.sub.4 Me H --CH═NOCH(CH.sub.3)-- 0                  ______________________________________                                    

                  TABLE 24                                                        ______________________________________                                        No    R.sup.2      R.sup.3                                                                             R.sup.4                                                                           M            n                                   ______________________________________                                        366   4-Br--C.sub.6 H.sub.4                                                                      Me    H   --CH═NOCH(CH.sub.3)--                                                                  0                                     367 3-Me-C.sub.6 H.sub.4 Me H --CH═NOCH(CH.sub.3)-- 0                     368 4-Me-C.sub.6 H.sub.4 Me H --CH═NOCH(CH.sub.3)-- 0                     369 4-Et-C.sub.6 H.sub.4 Me H --CH═NOCH(CH.sub.3)-- 0                     370 3-MeO-C.sub.6 H.sub.4 Me H --CH═NOCH(CH.sub.3)-- 0                    371 4-MeO-C.sub.6 H.sub.4 Me H --CH═NOCH(CH.sub.3)-- 0                    372 3-CF.sub.3 --C.sub.6 H.sub.4 Me H --CH═NOCH(CH.sub.3)-- 0                                                      373 4-CF.sub.3 --C.sub.6                                                     H.sub.4 Me H --CH═NOCH(CH.su                                              b.3)-- 0                              374 3,4-F.sub.2 --C.sub.6 H.sub.3 Me H --CH═NOCH(CH.sub.3)-- 0                                                     375 3,5-F.sub.2 --C.sub.6                                                    H.sub.3 Me H --CH═NOCH(CH.su                                              b.3)-- 0                              376 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H --CH═NOCH(CH.sub.3)-- 0                                                    377 3,5-Cl.sub.2--C.sub.6                                                    H.sub.3 Me H --CH═NOCH(CH.su                                              b.3)-- 0                              378 3,4-Me.sub.2 -C.sub.6 H.sub.3 Me H --CH═NOCH(CH.sub.3)-- 0                                                     379 4-Cl-3-Me-C.sub.6 H.sub.3                                                Me H --CH═NOCH(CH.sub.3)--                                                0                                     380 C.sub.6 H.sub.5 Me H --CH═NOCH.sub.2 -- 0                             381 C.sub.6 H.sub.5 Me H --CH═NN═C(CH.sub.3)-- 0                      382 4-F--C.sub.6 H.sub.4 Me H --CH═NN═C(CH.sub.3)-- 0                 383 3-F--C.sub.6 H.sub.4 Me H --CH═NN═C(CH.sub.3)-- 0                 384 3-Cl--C.sub.6 H.sub.4 Me H --CH═NN═C(CH.sub.3)-- 0                385 4-Cl--C.sub.6 H.sub.4 Me H --CH═NN═C(CH.sub.3)-- 0                386 4-Br--C.sub.6 H.sub.4 Me H --CH═NN═C(CH.sub.3)-- 0              ______________________________________                                    

                  TABLE 25                                                        ______________________________________                                        No    R.sup.2      R.sup.3                                                                             R.sup.4                                                                           M            n                                   ______________________________________                                        387   3-Me-C.sub.6 H.sub.4                                                                       Me    H   --CH═NN═C(CH.sub.3)--                                                              0                                     388 4-Me-C.sub.6 H.sub.4 Me H --CH═NN═C(CH.sub.3)-- 0                 389 4-Et-C.sub.6 H.sub.4 Me H --CH═NN═C(CH.sub.3)-- 0                 390 3-MeO-C.sub.6 H.sub.4 Me H --CH═NN═C(CH.sub.3)-- 0                391 4-MeO-C.sub.6 H.sub.4 Me H --CH═NN═C(CH.sub.3)-- 0                392 3-CF.sub.3 --C.sub.6 H.sub.4 Me H --CH═NN═C(CH.sub.3)-- 0                                                  393 4-CF.sub.3 --C.sub.6                                                     H.sub.4 Me H --CH═NN═C(C                                              H.sub.3)-- 0                          394 3,4-F.sub.2 --C.sub.6 H.sub.3 Me H --CH═NN═C(CH.sub.3)-- 0                                                 395 3,5-F.sub.2 --C.sub.6                                                    H.sub.3 Me H --CH═NN═C(C                                              H.sub.3)-- 0                          396 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H --CH═NN═C(CH.sub.3)-- 0       397 3,5-Cl.sub.2 --C.sub.6 H.sub.3 Me H --CH═NN═C(CH.sub.3)-- 0       398 3,4-Me.sub.2 -C.sub.6 H.sub.3 Me H --CH═NN═C(CH.sub.3)-- 0                                                 399 4-Cl-3-Me--C.sub.6 H.sub.3                                               Me H --CH═NN═C(CH.sub.3)                                              -- 0                                  400 3-Ph--C.sub.6 H.sub.4 Me H --CH═NN═C(CH.sub.3)-- 0                401 C.sub.6 H.sub.5 Me H --S--C(CH.sub.3)═N-- 1                           402 4-F--C.sub.6 H.sub.4 Me H --S--C(CH.sub.3)═N-- 1                      403 3-F--C.sub.6 H.sub.4 Me H --S--C(CH.sub.3)═N-- 1                      404 3-Cl--C.sub.6 H.sub.4 Me H --S--C(CH.sub.3)═N-- 1                     405 4-Cl--C.sub.6 H.sub.4 Me H --S--C(CH.sub.3)═N-- 1                     406 4-Br--C.sub.6 H.sub.4 Me H --S--C(CH.sub.3)═N-- 1                     407 3-Me-C.sub.6 H.sub.4 Me H --S--C(CH.sub.3)═N-- 1                    ______________________________________                                    

                  TABLE 26                                                        ______________________________________                                        No    R.sup.2      R.sup.3                                                                             R.sup.4                                                                           M            n                                   ______________________________________                                        408   4-Me-C.sub.6 H.sub.4                                                                       Me    H   --S--C(CH.sub.3)═N--                                                                   1                                     409 4-Et-C.sub.6 H.sub.4 Me H --S--C(CH.sub.3)═N-- 1                      410 3-MeO-C.sub.6 H.sub.4 Me H --S--C(CH.sub.3)═N-- 1                     411 4-MeO-C.sub.6 H.sub.4 Me H --S--C(CH.sub.3)═N-- 1                     412 3-CF.sub.3 --C.sub.6 H.sub.4 Me H --S--C(CH.sub.3)═N-- 1                                                       413 4-CF.sub.3 --C.sub.6                                                     H.sub.4 Me H --S--C(CH.sub.3).db                                              d.N-- 1                               414 3,4-F.sub.2 --C.sub.6 H.sub.3 Me H --S--C(CH.sub.3)═N-- 1                                                      415 3,5-F.sub.2 --C.sub.6                                                    H.sub.3 Me H --S--C(CH.sub.3).db                                              d.N-- 1                               416 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H --S--C(CH.sub.3)═N-- 1                                                     417 3,5-Cl.sub.2 --C.sub.6                                                   H.sub.3 Me H --S--C(CH.sub.3).db                                              d.N-- 1                               418 3,4-Me.sub.2 -C.sub.6 H.sub.3 Me H --S--C(CH.sub.3)═N-- 1                                                      419 4-Cl-3-Me-C.sub.6 H.sub.3                                                Me H --S--C(CH.sub.3)═N-- 1       420 3-Ph--C.sub.6 H.sub.4 Me H --S--C(CH.sub.3)═N-- 1                     421 C.sub.6 H.sub.5 Me H --ON═CH-- 1                                      422 4-F--C.sub.6 H.sub.4 Me H --ON═CH-- 1                                 423 3-F--C.sub.6 H.sub.4 Me H --ON═CH-- 1                                 424 3-Cl--C.sub.6 H.sub.4 Me H --ON═CH-- 1                                425 4-Cl--C.sub.6 H.sub.4 Me H --ON═CH-- 1                                426 4-Br--C.sub.6 H.sub.4 Me H --ON═CH-- 1                                427 3-Me-C.sub.6 H.sub.4 Me H --ON═CH-- 1                                 428 4-Me-C.sub.6 H.sub.4 Me H --ON═CH-- 1                               ______________________________________                                    

                  TABLE 27                                                        ______________________________________                                        No    R.sup.2       R.sup.3                                                                             R.sup.4                                                                             M        n                                    ______________________________________                                        429   4-Et-C.sub.6 H.sub.4                                                                        Me    H     --ON═CH--                                                                          1                                      430 3-MeO-C.sub.6 H.sub.4 Me H --ON═CH-- 1                                431 4-MeO-C.sub.6 H.sub.4 Me H --ON═CH-- 1                                432 3-CF.sub.3 --C.sub.6 H.sub.4 Me H --ON═CH-- 1                         433 4-CF.sub.3 --C.sub.6 H.sub.4 Me H --ON═CH-- 1                         434 3,4-F.sub.2 --C.sub.6 H.sub.3 Me H --ON═CH-- 1                        435 3,5-F.sub.2 --C.sub.6 H.sub.3 Me H --ON═CH-- 1                        436 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H --ON═CH-- 1                       438 314-Me.sub.2 -C.sub.6 H.sub.3 Me H --ON═CH-- 1                        439 3-F--C.sub.6 H.sub.4 Et H O 1                                             440 4-F--C.sub.6 H.sub.4 Et H O 1                                             441 2-Cl--C.sub.6 H.sub.4 Et H O 1                                            442 3-Cl--C.sub.6 H.sub.4 Et H O 1                                            443 4-Cl--C.sub.6 H.sub.4 Et H O 1                                            444 2-Me-C.sub.6 H.sub.4 Et H O 1                                             445 3-Me-C.sub.6 H.sub.4 Et H O 1                                             446 4-Me-C.sub.6 H.sub.4 Et H O 1                                             447 3-CF.sub.3 --C.sub.6 H.sub.4 Et H O 1                                     448 2,5-Me.sub.2 -C.sub.6 H.sub.3 Et H O 1                                    449 4-Cl-2-Me-C.sub.6 H.sub.3 Et H O 1                                        450 2,5-Cl.sub.2 -C.sub.6 H.sub.3 Et H O 1                                  ______________________________________                                    

                  TABLE 28                                                        ______________________________________                                        No    R.sup.2      R.sup.3                                                                             R.sup.4                                                                           M            n                                   ______________________________________                                        451   4-Cl--C.sub.6 H.sub.4                                                                      Et    H   --ON═C(Me)-                                                                            1                                     452 3-CF.sub.3 --C.sub.6 H.sub.4 Et H --ON═C(Me)- 1                       453 4-CF.sub.3 --C.sub.6 H.sub.4 Et H --ON═C(Me)- 1                       454 4-Me-C.sub.6 H.sub.4 Et H --ON═C(Me)- 1                               455 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Et H --ON═C(Me)- 1                     456 4-Cl--C.sub.6 H.sub.4 Et H --ON═C(SMe)- 1                             457 3-CF.sub.3 --C.sub.6 H.sub.4 Et H --ON═C(SMe)- 1                      458 4-CF.sub.3 --C.sub.6 H.sub.4 Et H --ON═C(SMe)- 1                      459 4-Me-C.sub.6 H.sub.4 Et H --ON═C(SMe)- 1                              460 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Et H --ON═C(SMe)- 1                    461 4-Cl--C.sub.6 H.sub.4 Et H --CH═NOCH(CH.sub.3)-- 0                    462 3-CF.sub.3 --C.sub.6 H.sub.4 Et H --CH═NOCH(CH.sub.3)-- 0                                                      463 4-CF.sub.3 --C.sub.6                                                     H.sub.4 Et H --CH═NOCH(CH.su                                              b.3)-- 0                              464 4-Me-C.sub.6 H.sub.4 Et H --CH═NOCH(9H3)-- 0                          465 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Et H --CH═NOCH(CH.sub.3)-- 0                                                    466 4-Cl--C.sub.6 H.sub.4 Et H                                               --CH═NN═C(CH.sub.3)-- 0       467 3-CF.sub.3 --C.sub.6 H.sub.4 Et H --CH═NN═C(CH.sub.3)-- 0                                                  468 4-CF.sub.3 --C.sub.6                                                     H.sub.4 Et H --CH═NN═C(C                                              H.sub.3)-- 0                          469 4-Me-C.sub.6 H.sub.4 Et H --CH═NN═C(CH.sub.3)-- 0                 470 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Et H --CH═NN═C(CH.sub.3)-- 0       471 4-Ph--C.sub.6 H.sub.4 Et H O 1                                          ______________________________________                                    

                  TABLE 29                                                        ______________________________________                                        No   R.sup.2         R.sup.3                                                                             R.sup.4                                                                           M           n                                  ______________________________________                                        472  C.sub.6 H.sub.5 Et    H   O           0                                    473 C.sub.6 H.sub.5 Me H --CH═NOC(CH.sub.3).sub.2-- 0                     474 4-F--C.sub.6 H.sub.4 Me H --CH═NOC(CH.sub.3).sub.2-- 0                475 3-F--C.sub.6 H.sub.4 Me H --CH═NOC(CH.sub.3).sub.2-- 0                476 3-Cl--C.sub.6 H.sub.4 Me H --CH═NOC(CH.sub.3).sub.2-- 0                                                         477 4-Cl--C.sub.6 H.sub.4 Me                                                 H --CH═NOC(CH.sub.3).sub.2-                                               - 0                                  478 4-Br--C.sub.6 H.sub.4 Me H --CH═NOC(CH.sub.3).sub.2-- 0                                                         479 3-Me-C.sub.6 H.sub.4 Me H                                                --CH═NOC(CH.sub.3).sub.2--                                                0                                    480 4-Me-C.sub.6 H.sub.4 Me H --CH═NOC(CH.sub.3).sub.2-- 0                481 4-Et-C.sub.6 H.sub.4 Me H --CH═NOC(CH.sub.3).sub.2-- 0                482 3-MeO-C.sub.6 H.sub.4 Me H --CH═NOC(CH.sub.3).sub.2-- 0                                                         483 4-MeO-C.sub.6 H.sub.4 Me                                                 H --CH═NOC(CH.sub.3).sub.2-                                               - 0                                  484 3-CF.sub.3 --C.sub.6 H.sub.4 Me H --CH═NOC(CH.sub.3).sub.2-- 0                                                  485 4-CF.sub.3 --C.sub.6                                                     H.sub.4 Me H --CH═NOC(CH.su                                               b.3).sub.2-- 0                       486 3,4-F.sub.2 --C.sub.6 H.sub.3 Me H --CH═NOC(CH.sub.3).sub.2-- 0       487 3,5-F.sub.2 --C.sub.6 H.sub.3 Me H --CH═NOC(CH.sub.3).sub.2-- 0       488 3,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H --CH═NOC(CH.sub.3).sub.2--                                                 0                                    489 3,5-Cl.sub.2 --C.sub.6 H.sub.3 Me H --CH═NOC(CH.sub.3).sub.2 --                                                0                                    490 3,4-Me.sub.2 --C.sub.6 H.sub.3 Me H --CH═NOC(CH.sub.3).sub.2--                                                 0                                    491 4-Cl-3-Me-C.sub.6 H.sub.3 Me H --CH═NOC(CH.sub.3).sub.2 -- 0                                                    492 6-(2-CN--PhO)-4-primidyl                                                 Et H O 0                           ______________________________________                                    

                  TABLE 30                                                        ______________________________________                                        No   R.sup.2     R.sup.3                                                                              R.sup.4                                                                            M             n                                  ______________________________________                                        493  2-Cl--C.sub.6 H.sub.4                                                                     Me     H    --CH═NOCH(CH.sub.3)--                                                                   0                                    494 2,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H --CH═NOCH(CH.sub.3)-- 0                                                     495 3-CF.sub.3 O--C.sub.6                                                    H.sub.3 Me H --CH═NOCH(CH.s                                               ub.3)-- 0                            496 4-CF.sub.3 O--C.sub.6 H.sub.3 Me H --CH═NOCH(CH.sub.3)-- 0                                                      497 2-pyridyl Me H --CH═NO                                               CH(CH.sub.3)-- 0                     498 3-pyridyl Me H --CH═NOCH(CH.sub.3)-- 0                                499 4-pyridyl Me H --CH═NOCH(CH.sub.3)-- 0                                500 2-furyl Me H --CH═NOCH(CH.sub.3)-- 0                                  501 2-thienyl Me H --CH═NOCH(CH.sub.3)-- 0                                502 3-isoxazolyl Me H --CH═NOCH(CH.sub.3)-- 0                             503 2,4-Cl.sub.2 --C.sub.6 H.sub.3 Me H --CH═NN═C(CH.sub.3)-- 0       504 3-CF.sub.3 O--C.sub.6 H.sub.3 Me H --CH═NN═C(CH.sub.3)-- 0                                                  505 4-CF.sub.3 O--C.sub.6                                                    H.sub.3 Me H --CH═NN═C(                                               CH.sub.3)-- 0                        506 2-pyridyl Me H --CH═NN═C(CH.sub.3)-- 0                            507 3-pyridyl Me H --CH═NN═C(CH.sub.3)-- 0                            508 4-pyridyl Me H --CH═NN═C(CH.sub.3)-- 0                            509 2-furyl Me H --CH═NN═C(CH.sub.3)-- 0                              510 2-thienyl Me H --CH═NN═C(CH.sub.3)-- 0                            511 3-isoxazolyl Me H --CH═NN═C(CH.sub.3)-- 0                         512 2-Cl--C.sub.6 H.sub.4 Me H --CH═NN═C(CH.sub.3)-- 0              ______________________________________                                    

                                      TABLE 31                                    __________________________________________________________________________    No Physical data                                                              __________________________________________________________________________    A-12                                                                             .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.19(3H, s), 2.23(3H, s),               3.44(3H, s), 5.05(1H, d, J=12.2),                                             5.14(1H, d, J=12.2), 5.69(1H, s), 5.90(1H, s), 6.85-6.91(2H, m),              7.13-7.18(2H, m),                                                             7.37-7.56(4H, m).                                                            A-22 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.23(3H, s), 3.43(3H, s),           5.11(1H, d, J=11.6), 5.17(1H, d,                                              J=11.6), 5.63(1H, s), 5.91(1H, s), 7.03-7.58(8H, m).                         A-31 mp 78.5˜79.5° C.                                            A-32 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.24(3H, s), 3.43(3H, s),           5.05(1H, d, J=12.2), 5.11(1H, d,                                              J=12.2), 5.60(1H, s), 5.90(1H, s), 6.74(1H, dd, J=8.5, 2.4), 7.00(1H,         d, J=3.1), 7.30-                                                              7.57(5H, m).                                                                 A-36 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.14(3H, s), 2.23(3H, s),           2.32(3H, s), 3.44(3H, s), 5.03(1H,                                            d, J=12.2), 5.12(1H, d, J=11.6), 5.69(1H, s), 5.90(1H, s), 6.69-6.71(2H       , m), 7.12(1H,                                                                d, J=7.3), 7.34-7.57(4H, m).                                                 A-41 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.16(3H, s), 2.23(3H, s),           3.43(3H, s), 5.04(1H, d, J=11.6),                                             5.11(1H, d, J=12.2), 5.64(1H, s), 5.90(1H, s), 6.75(1H, d, J=8.5),            7.07-7.11(2H, m),                                                             7.35-7.55(4H, m).                                                            A-44 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.24(3H, s), 3.45(3H, s),           5.11(1H, d, J=11.6), 5.19(1H, d,                                              J=11.6), 5.69(1H, s), 5.92(1H, s), 6.97-7.00(2H, m), 7.27-7.61(11H,           m).                                                                          A-55 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.06(3H, s), 2.23(6H, s),           2.29(3H, s), 3.43(3H, s), 5.00(1H,                                            d, J=11.6), 5.10(1H, d, J=11.6), 5.69(1H, s), 5.89(1H, s), 6.58(1H,           s), 6.64(1H, s),                                                              7.35-7.57(4H, m).                                                            A-65 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.34(3H, s), 3.45(3H, s),           5.48(2H, s), 5.80(1H, s), 5.90(1H,                                            s), 7.34-7.56(4H, m), 7.64(1H, d, J=2.4), 7.99(1H, d, J=2.4).                A-66 mp 57˜5.59° C.                                              A-67 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.24(3H, s), 3.45(3H, s),           5.53(1H, d, J=12.7), 5.57(1H,                                                 J=13.0), 5.82(1H, s), 5.91(1H, s), 6.98(1H, dd, J=6.8, 5.1), 7.34-7.52(       4H, m),                                                                       7.87(1H, d, J=7.3), 8.31(1H, d, J=5.1).                                      A-68 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.25(3H, s), 3.45(3H, s),           5.52(2H, s), 5.77(1H, s), 5.92(1H,                                            s), 7.33-7.54(4H, m), 7.84(1H, d, J=2.6), 8.25(1H, d, 2.5).                  A-69 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.24(3H, s), 3.46(3H, s),           5.57(2H, s), 5.79(1H, s), 5.91(1H,                                            s), 7.35-7.56(4H, m), 7.85(1H, d, J=2.2), 8.33(1H, t, J=1.2).                A-76 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.25(3H, s), 3.45(3H, s),           5.63(1H, d, J=12.2), 5.70(1H, d,                                              J=12.2), 5.72(1H, s), 5.95(1H, s), 7.32-7.62(7H, m).                         A-87 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.10(3H, s), 2.21(3H, s),           3.42(3H, s), 5.29(2H, s), 5.77(1H,                                            s), 5.86(1H, s), 7.30-7.60(8H, m).                                         __________________________________________________________________________

                                      TABLE 32                                    __________________________________________________________________________    No  Physical data                                                             __________________________________________________________________________    A-102                                                                             .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.16(3H, s), 2.21(3H, s),               3.43(3H, s), 5.32(2H, s), 5.77(1H,                                           s), 5.87(1H, s), 7.33-7.64(6H, m), 7.80(1H, d, J=7.9), 7.87(1H, s).             A-103 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.15(3H, s), 2.21(3H,            s), 3.43(3H, s), 5.32(2H, s), 5.77(1H,                                       s), 5.87(1H, s), 7.36-7.74(8H, m).                                           A-110 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.10(3H, s), 2.21(3H, s),           3.43(3H, s), 5.30(2H, s), 5.75(1H,                                           s), 5.87(1H, s), 7.33-7.58(6H, m), 7.71(1H, d, J=1.8).                       A-147 mp 68˜73° C.                                               A-241 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.24(3H, s), 3.42(3H, s),           5.81(1H, s), 5.94(1H, s), 6.85-                                              7.60(9H, m).                                                                 A-323 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.18(6H, d, J=6.1),                 1.83(3H, s), 2.24(3H, s), 2.31(2H, dd,                                       J=12.8, 11.0), 3.42-3.68(7H, m), 4.96(1H, d, J=12.2), 5.01(1H, d,              J=12.2), 7.29-                                                               7.55(4H, m).                                                                 A-327 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 0.66(1H, q, J=12.8),                0.86(6H, d, J=6.7), 1.57-1.82(3H, m),                                        1.84(3H, s), 2.03(2H, t, J=12.8), 2.23(3H, s), 3.42(3H, s), 3.63(2H,           dd, J=12.2,                                                                  3.7), 4.94(1H, d, J=11.6), 5.00(1H, d, J=11.6), 5.78(1H, s), 5.84(1H,          s), 7.31-                                                                    7.55(4H, m).                                                                 A-361 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.56(1.61)(3H, d, J=6.7),           2.16(2.23)(3H, s), 3.27(3.39                                                 (3H, s), 5.26-5.35(1H, m), 5.57(5.69)(1H, s), 5.79(5.91)(1H, s),               7.27-7.63(9H, m),                                                            8.30(8.35)(1H, s).                                                           A-373 .sup.1 H-NMR(CDCl.sub.3) ppm: 1.57-1.60(3H, m), 2.14(2.23)(3H,            s), 3.26(3.39)(3H, s),                                                       5.34(1H, sept, J=6.7), 5.57(5.68)(1H, s), 5.69(5.86)(1H, s), 7.33-7.64(        8H, m),                                                                      8.32(8.37)(1H, s).                                                           A-385 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.22(3H, s), 2.41 (3H, s),          3.48(3H, s), 5.79(1H, s), 6.28(1H,                                           s), 7.38-7.90(8H, m), 8.66(1H, s).                                           A-393 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.23(3H, s), 2.44(3H, s),           3.49(3H, s), 5.81(1H, s), 6.26(1H,                                           s), 7.43-8.02(8H, m), 8.57(1H, s).                                           A-448 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.25(3H, t, J=7.3),                 2.15(3H, s), 2.23(3H, s), 2.32(3H, s),                                       3.55-3.65(2H, m), 5.03(1H, d, J=11.6), 5.13(1H, d, J=11.6), 5.79(1H,           s), 5.91(1H,                                                                 s), 6.68-6.71(2H, m) 7.02(1H, d, J=7.3), 7.36-7.57(4H, m).                   A-449 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.25(3H, t, J=7.3),                 2.16(3H, s), 2.23(3H, s), 3.50-3.67(2H,                                      m), 5.05(1H, d, J=12.2), 5.11(1H, d, J=12.2), 5.74(1H, s), 5.90(1H,            s), 6.75(1H, d,                                                              J=8.5), 7.06-7.11(2H, m), 7.33-7.58(4H, m).                                  A-471 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.26(3H, t, J=6.7),                 2.24(3H, s), 3.56-3.64(2H, m), 5.12(1H,                                      d, J=12.2), 5.19(1H, d, J=11.6), 5.79(1H, s), 5.92(1H, s), 6.95-7.01(2H        , m), 7.28-                                                                  7.64(11H, m).                                                                A-472 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.22(3H, t, J=7.3),                 2.23(3H, s), 3.54-3.63(2H, m), 5.91(1H,                                      s), 5.94(1H, s), 6.88-7.34(8H, m), 7.59(1H, dd, J=7.9, 1.8).               __________________________________________________________________________

                                      TABLE 33                                    __________________________________________________________________________    No Physical data                                                              __________________________________________________________________________    B-36                                                                              .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.21(3H, t, J=7.9), 2.13(3H,            s), 2.32(3H, s), 2.63(2H, q,                                                 J=7.9), 3.44(3H, s), 5.03(1H, d, J=11.6), 5.12(1H, d, J=11.6),                 5.70(1H, s), 5.93(1H,                                                        s), 6.69-6.79(2H, m), 7.02(1H, d, J=7.9), 7.25-7.58(4H, m).                  C-36 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.81(3H, s), 2.16(3H, s),            2.34(3H, s), 2.74-2.79(2H, m),                                               3.29(3H, s), 4.64(1H, d, J=6.1), 4.87-4.96(1H, m), 5.07(1H, d,                 J=11.0), 5.16(1H, d,                                                         J=11.6), 6.72(1H, d, J=7.3), 6.79(1H, s), 7.03(1H, d, J=7.3), 7.33-7.52        (4H, m).                                                                    D-36 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.19(3H, s), 2.32(3H, s),            3.43(3H, s), 5.02(1H, d, J=12.2),                                            5.20(1H, d, J=12.2), 5.80(1H, s), 6.32(1H, d, J=1.8), 6.68-6.70(2H,            m), 7.12(1H, d,                                                              J=7.9), 7.32-7.63(4H, m), 8.32(1H, d, J=1.2).                                D-41 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.20(3H, s), 3.42(3H, s),            5.01(1H, d, J=12.2), 5.18(1H, d,                                             J=12.2), 5.76(1H, s), 6.31(1H, d, J=1.8), 6.77(1H, d, J=8.6), 7.07-7.12        (2H, m),                                                                     7.3214 7.64(4H, m), 8.32(1H, d, J=1.8).                                      D-65 mp 86˜87° C.                                                D-66 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 3.42(3H, s), 5.45(1H, d,             J=12.8), 5.57(1H, d, J=12.8),                                                5.87(1H, s), 6.32(1H, d, J=1.2), 6.79(1H, d, J=8.6), 7.32-7.79(5H, m),         8.32(1H, d,                                                                  J=1.2), 8.44(1H, s).                                                         D-67 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 3.44(3H, s), 5.52(1H, d,             J=13.4), 5.64(1H, d, J=13.4),                                                5.94(1H, s), 6.31(1H, d, J=1.8), 6.98(1H, dd, J=7.3, 4.9), 7.31-7.63(4H        , m),                                                                        7.87(1H, d, J=7.9), 8.31-8.32(2H, m).                                        D-68 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 3.43(3H, s), 5.59(1H, d,             J=12.8), 5.61(1H, d, J=12.8),                                                5.90(1H, s), 6.31(1H, d, J=1.8), 7.31-7.63(4H, m), 7.84(1H, d, J=2.4),         8.26(1H, d,                                                                  J=2.4), 8.32(1H, d, J=1.8).                                                  D-69 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 3.45(3H, s), 5.55(1H, d,             J=12.8), 5.63(1H, d, J=12.8),                                                5.93(1H, s), 6.33(1H, d, J=1.2), 7.32-7.65(4H, m), 7.85(1H, d, J=1.8),         8.32-                                                                        8.33(2H, m).                                                                 D-70 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 3.44(3H, s), 5.63(1H, d,             J=12.2), 5.76(1H, d, J=12.2),                                                5.89(1H, s), 6.34(1H, d, J=1.8), 7.20-7.72(8H, m), 8.33(1H, d, J=1.2).       D-84 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.18(3H, s), 3.41(3H, s),            5.23(1H, d, J=12.2), 5.4(1H, d,                                              J=12.2), 5.91(1H, s), 6.30(1H, d, J=1.2), 7.00-7.07(2H, m), 7.31-7.65(6        H,                                                                           m), 8.31(1H, d, J=1.8).                                                      D-87 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.17(3H, s), 3.41(3H, s),            5.24(1H, d, J=12.2), 5.31(1H, d,                                             J=12.2), 5.91(1H, s), 6.30(1H, d, J=1.8), 7.29-7.65(8H, m), 8.31(1H,           d, J=1.8).                                                                  D-94 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.18(3H, s), 2.35(3H, s),            3.41(3H, s), 5.23(1H, d, J=12.2),                                            5.40(1H, d, J=12.2), 5.92(1H, s), 6.29(1H, d, J=1.8), 7.17-7.61(8H,            m), 8.30(1H, d,                                                              J=1.8).                                                                    __________________________________________________________________________

                                      TABLE 34                                    __________________________________________________________________________    No  Physical data                                                             __________________________________________________________________________    D-103                                                                             .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.21(3H, s), 3.42(3H, s),               5.27(1H, d, J=12.2), 5.44(1H, d,                                             J=12.2), 5.91(1H, s), 6.30(1H, d, J=1.2), 7.31-7.56(8H, m), 8.31(1H,           d, J=1.2).                                                                  D-110 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.15(3H, s), 3.42(3H, s),           5.25(1H, d, J=12.8), 5.42(1H, d,                                             J=12.8), 5.89(1H, s), 6.30(1H, d, J=1.2), 7.31-7.64(6H, m), 7.73(1H,           d, J=1.8),                                                                   8.31(1H, d, J=1.8).                                                          D-147 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.09(3H, s), 3.42(3H, s),           5.25(1H, d, J=12.2), 5.45(1H, d,                                             J=12.8), 5.93(1H, s), 6.30(1H, d, J=1.8), 7.30-7.61(6H, m), 8.30(1H,           d, J=1.8).                                                                  D-154 mp 73.5˜74.5° C.                                           D-323 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.18(6H, d, J=6.1),                 1.89(3H, s), 2.31(2H, dd, J=12.8,                                            10.4), 3.40(3H, s), 3.45(2H, d, J=11.6), 3.57-3.68(2H, m), 4.94(1H, d,         J=11.6),                                                                     5.10(1H, d, J=12.2), 5.89(1H, s), 6.28(1H, d, J=1.8), 7.28-7.59(4H,            m), 8.30(1H,                                                                 d, J=1.8).                                                                   D-448 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.26(3H, t, J=7.3),                 2.19(3H, s), 2.31(3H, s), 3.54-3.63(2H,                                      m), 5.02(1H, d, J=12.2), 5.21(1H, d, J=12.2), 5.91(1H, s), 6.33(1H, d,         J=1.8),                                                                      6.69(2H, brs), 7.02(1H, d, J=7.9), 7.31-7.65(4H, m), 8.31(1H, d,               J=1.2).                                                                     D-449 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.26(3H, t, J=7.3),                 2.20(3H, s), 3.53-3.61(2H, m), 5.02(1H,                                      J=12.8), 5.19(1H, d, J=12.2), 5.86(1H, s), 6.33(1H, d, J=1.2),                 6.77(1H, d, J=8.6),                                                          7.07-7.12(2H, m), 7.32-7.67(4H, m), 8.32(1H, d, J=1.2).                      E-12 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.25(3H, s), 2.36(3H, s),            3.42(3H, s), 5.02(1H, d, J=12.2),                                            5.22(1H, d, J=12.2), 5.69(1H, s), 5.91(1H, s), 6.85-6.90(2H, m),               7.13-7.17(2H, m),                                                            7.32-7.64(4H, m).                                                            E-36 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.20(3H, s), 2.31(3H, s),            2.36(3H, s), 3.42(3H, s), 5.01(1H,                                           d, J=12.2), 5.20(1H, d, J=12.2), 5.69(1H, s), 5.91(1H, s), 6.68-6.70(2H        , m),                                                                        7.02(1H, d, J=7.9), 7.31-7.63(4H, m).                                        E-65 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.35(3H, s), 3.39(3H, s),            5.45(1H, d, J=12.8), 5.53(1H, d,                                             J=12.8), 5.82(1H, s), 5.91(1H, s), 7.26-7.65(5H, m), 8.00(1H, d,               J=2.4).                                                                     E-66 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.36(3H, s), 3.36(3H, s),            5.44(1H, d, J=12.8), 5.57(1H, d,                                             J=12.2), 5.77(1H, s), 5.92(1H, s), 6.80(1H, d, J=8.5), 7.30-7.79(5H,           m), 8.45(1H,                                                                 s).                                                                          E-67 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.36(3H, s), 3.43(3H, s),            5.51(1H, d, J=13.4), 5.65(1H, d,                                             J=13.4), 5.83(1H, s), 5.91(1H, s), 6.98(1H, dd, J=7.3, 4.9), 7.29-7.63(        4H, m),                                                                      7.86-7.88(1H, m), 8.31-8.33(1H, m).                                          E-68 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.36(3H, s), 3.42(3H, s),            5.48(1H, d, J=13.4), 5.62(1H, d,                                             J=12.8), 5.79(1H, s), 5.91(1H, s), 7.30-7.63(4H, m), 7.84(1H, d,               J=2.4), 8.26(1H,                                                             d, J=2.4).                                                                   E-69 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.36(3H, s) 3.39(3H, s),             5.54(1H, d, J=12.8), 5.62(1H, d,                                             J=12.8), 5.82(1H, s), 5.92(1H, 5) 7.31-7.65(4H, m), 7.85(1H, d,                J=2.4), 8.33(1H,                                                             d, J=2.4).                                                                 __________________________________________________________________________

                                      TABLE 35                                    __________________________________________________________________________    No  Physical data                                                             __________________________________________________________________________    E-87                                                                              .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.18(3H, s), 2.32(3H, s),               3.40(3H, s), 5.22(1H, d, J=12.8),                                            5.31(1H, d, J=12.8), 5.80(1H, s), 5.90(1H, s), 7.30-7.62(8H, m).                E-100 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.18(3H, s), 2.35(3H,            s), 3.40(3H, s), 3.82(3H, s), 5.21(1H,                                       d, J=12.8), 5.40(1H, d, J=12.8), 5.82(1H, s), 5.90(1H, s), 6.85-6.90(2H        , m), 7.31-                                                                  7.61(6H, m).                                                                 E-103 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.22(3H, s), 2.35(3H, s),           3.41(3H, s), 5.25(1H, d, J=12.2),                                            5.44(1H, d, J=12.2), 5.80(1H, s), 5.91(1H, s), 7.32-7.76(8H, m).                E-110 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.16(3H, s), 2.35(3H,            s), 3.44(3H, s), 5.23(1H, d, J=12.2),                                        5.42(1H, d, J=12.8), 5.79(1H, s), 5.91(1H, s), 7.32-7.60(5H, m),               7.63(1H, J=1.8),                                                             7.72(1H, d, J=1.2).                                                          E-323 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.18(6H, d, J=6.7),                 1.90(3H, s), 2.31(2H, dd, J=12.8, 10.4),                                     2.35(3H, s), 3.40(3H, s), 3.46(2H, dd, J=13.4, 1.0), 3.57-3.68(2H, m),         4.92(1H, d,                                                                  J=12.2), 5.11(1H, d, J=12.2), 5.78(1H, s), 5.89(1H, s), 7.30-7.60(4H,          m).                                                                         F-36 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.21(3H, s), 2.33(3H, s),            2.68-2.82(1H, m), 2.95-3.08(1H,                                              m), 3.42(3H, s), 4.17-4.35(2H, m), 4.99(1H, d, J=12.2), 5.21(1H, d,            J=11.6),                                                                     5.51(1H, s), 6.70(1H, d, J=7.3), 6.75(1H, s), 7.03(1H, d, J=7.3),              7.36-7.61 (4H, m).                                                          F-41 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.23(3H, s), 2.65-2.79(1H,           m), 2.94-3.08(1H, m), 3.41(3H,                                               s), 4.18-4.36(2H, m), 4.99(1H, d, J=12.2), 5.21(1H, d, J=12.2),                5.47(1H, s),                                                                 6.84(1H, d, J=8.6), 7.09-7.13(2H, m), 7.34-7.61(4H, m).                      F-55 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.13(3H, s), 2.24(3H, s),            2.30(3H, s), 2.68-3.08(2H, m),                                               3.41(3H, s), 4.18-4.35(2H, m), 4.96(1H, d, J=12.2), 5.19(1H, d,                J=12.2), 5.51(1H,                                                            s), 6.64(2H, s), 7.36-7.64(4H, m).                                           F-66 mp 71˜72° C.                                                F-68 mp 126.5˜128° C.                                            F-69 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.67-2.81(1H, m), 2.94-3.08(1        H, m), 3.43(3H, s), 4.20-                                                    4.35(2H, m), 5.54(1H, d, J=12.8), 5.62(1H, d, J=12.2), 5.63(1H, s),            7.33-7.63(4H,                                                                m), 7.85(1H, d, J=1.8), 8.34(1H, d, J=1.2).                                  F-76 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.72-2.82(1H, m), 2.94-3.08(1        H, m), 3.42(3H, s), 4.22-                                                    4.37(2H, m), 5.57(1H, s), 5.60(1H, d, J=12.2), 5.75(1H, d, J=12.2),            7.31-7.62(7H,                                                                m).                                                                          F-87 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.21(3H, s), 2.65-2.79(1H,           m), 2.93-3.07(1H, m), 3.39(3H,                                               s), 4.17-4.34(2H, m), 5.20(1H, d, J=12.2), 5.42(1H, d, J=12.2),                5.60(1H, s), 7.29-                                                           7.60(8H, m).                                                               __________________________________________________________________________

                                      TABLE 36                                    __________________________________________________________________________    No  Physical data                                                             __________________________________________________________________________    F-103                                                                             .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.25(3H, s), 2.65-2.79(1H, m),          2.94-3.07(1H, m), 3.40(3H,                                                   s), 4.21-4.35(2H, m), 5.23(1H, d, J=12.2), 5.45(1H, d, J=12.8),                5.61(1H, s), 7.32-                                                           7.76(8H, m).                                                                 F-323 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.18(6H, d, J=6.1),                 1.94(3H, s), 2.31(2H, dd, J=12.8,                                            11.0), 2.65-3.05(2H, m), 3.39(3H, s), 3.46(2H, dd, J=12.8, 2.5),               3.55-3.70(2H, m),                                                            4.17-4.34(2H, m), 4.89(1H, d, J=11.6), 5.11(1H, d, J=12.2), 5.57(1H,           s), 7.29-                                                                    7.57(4H, m).                                                                 G-36 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.06(3H, s), 2.07(3H, s),            2.17(3H, s), 2.31(3H, s), 3.36(3H,                                           s), 4.91(1H, d, J=12.2), 4.97(1H, d, J=12.2), 5.51(1H, s), 6.61(1H,            s), 6.70(1H, d,                                                              J=7.3), 7.03(1H, d, J=7.9), 7.33-7.52(4H, m).                                G-448 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.26(3H, t, J=7.3),                 2.05(3H, s), 2.07(3H, s), 2.16(3H, s),                                       2.30(3H, s), 3.50(2H, qd, J=7.3, 1.8), 4.93(1H, d, J=12.2), 4.98(1H,           d, J=12.2),                                                                  5.62(1H, s), 6.61(1H, s), 6.70(1H, d, J=7.9), 7.03(1H, d, J=7.3),              7.33-4.55(4H, m).                                                           H-1 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.45(3H, s), 3.39(3H, s),             4.97(1H, d, J=11.0), 5.13(1H, d,                                             J=11.6), 5.86(1H, s), 6.82-6.86(2H, m), 6.99(1H, t, J=7.3), 7.28-7.52(6        H, m).                                                                      H-36 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.07(3H, s), 2.32(3H, s),            2.44(3H, s), 3.40(3H, s), 4.93(1H,                                           d, J=11.6), 5.09(1H, d, J=11.6), 5.88(1H, s), 6.63(1H, s), 6.71(1H, d,         J=7.3),                                                                      7.02(1H, d, J=7.3), 7.40-7.54(4H, m).                                        I-1 mp 66˜67.5° C.                                               I-12 mp 87˜88° C.                                                I-41 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.20(3H, s), 3.41(3H, s),            3.54(3H, s), 4.94(1H, d, J=12.8),                                            5.10(1H, d, J=12.8), 5.72(1H, s), 6.72(1H, d, J=8.6), 6.82(1H, d,              J=1.2), 5.95(1H,                                                             d, J=1.2), 7.04-7.54(6H, m).                                                 I-81 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.15(3H, s), 3.41(3H, s),            3.59(3H, s), 5.24(1H, d, J=12.2),                                            5.30(1H, d, J=12.2), 5.85(1H, s), 5.83(1H, s), 5.97(1H, d, J=1.2),             7.30-7.65(9H,                                                                m).                                                                        __________________________________________________________________________

                                      TABLE 37                                    __________________________________________________________________________    No  Physical data                                                             __________________________________________________________________________    I-449                                                                             .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.26(3H, t, J=7.3), 2.20(3H,            s), 3.46-3.64(2H, m), 3.55(3H,                                               s), 4.95(1H, d, J=12.8), 5.10(1H, d, J=12.8), 5.84(1H, s), 6.72(1H, d,         J=8.6),                                                                      6.82(1H, d, J=1.2), 6.94(1H, d, J=1.2), 7.04-7.54(6H, m).                    J-36 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.19(3H, s), 2.29(3H, s),            3.45(3H, s), 5.13(1H, d, J=12.3),                                            5.27(1H, d, J=12.3), 5.67(1H, s), 6.65(1H, s), 6.67(1H, d, J=7.3),             7.01 (1H, d, J=7.3),                                                         7.12-7.69(7H, m), 8.53(1H, dd, J=4.9, 1.8).                                  K-36 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.13(3H, s), 2.30(3H, s),            3.40(3H, s), 4.95(1H, d, J=12.2),                                            5.05(1H, d, J=1 2.2), 5.63(1H, s), 6.59(1H, s), 6.69(1H, d, J=7.3),            7.02(1H, d, J=7.3),                                                          7.20-7.64(6H, m), 8.50(1H, dd, J=4.9, 1.8), 8.56(1H, d, J=2.4).                 L-41 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.17(3H, s), 3.47(3H, s),         5.05(1H, d, J=12.2), 5.19(1H, d,                                             J=12.2), 5.94(1H, s), 6.83(1H, dd, J=7.3, 1.8), 7.10-7.13(2H, m),              7.40-7.71(4H, m),                                                            8.36(1H, s).                                                               __________________________________________________________________________

                                      TABLE 38                                    __________________________________________________________________________    No  Physical data                                                             __________________________________________________________________________    A-75                                                                              .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.21(3H, s), 3.35(3H, s),               5.51(1H, s), 5.91(1H, s), 6.87(1H,                                           s), 7.11(1H, dd, J=7.9, 1.2), 7.35-7.67(3H; m), 8.53(1H, s)                  A-258 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.18(3H, s), 3.37(3H, s),           5.57(1H, s), 5.89(1H, s), 7.15(1H,                                           dd, J=7.9, 1.8), 7.33-7.66(3H, m), 1.97(1H, d, J=1.8), 8.18(1H, s)              A-260 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.22(3H, s), 3.38(3H,            s), 5.58(1H, s), 5.95(1H, s), 6.49(1H,                                       s), 7.16(1H, dd, J=7.9, 1.2), 7.33-7.75(7H, m), 8.35(1H, s)                  A-365 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.53(1.57)(3H, d, J=6.7),           2.17(2.23)(3H, s), 3.30(3.39)                                                (3H, s), 5.22-5.31(1H, m), 5.56(5.74)(1H, s), 5.69(5.88)(1H, s),               7.24-7.65(8H, m),                                                            8.29(8.33)(1H, s)                                                            A-372 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.57(1.61)(3H, d, J=6.7),           2.17(2.23)(3H,.s), 3.28(3.39)(3H,                                            s), 5.29-5.39(1H, m), 5.62(5.72)(1H, s), 5.70(5.85)(1H, s), 7.31-7.65(5        H, m),                                                                       8.33(8.38)(1H, s)                                                            A-376 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.52(1.56)(3H, d, J=6.7),           2.18(2.23)(3H, s), 3.33(3.40)                                                (3H, s), 5.18-5.28(1H, m), 5.59(5.72)(1H, s), 5.70(5.86)(1H, s),               7.13-7.65(7H, m),                                                            8.31(8.34)(1H, s)                                                            A-381 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.22(3H, s), 2.43(3H, s),           3.48(3H, s), 5.80(1H, s), 6.30(1H,                                           s), 7.39-7.53(5H, m), 7.70(1H, d, J=7.3), 7.86-7.93(3H, m), 8.67(1H,           s)                                                                          A-382 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.22(3H, s), 2.42(3H, s),           3.48(3H, s), 5.79(1H, s), 6.29(1H,                                           s), 7.07-7.15(2H, m), 7.42-7.54(2H, m), 7.70(1H, dd, J=7.3, 1.2),              7.86-7.94(3H, m),                                                            8.67(1H, s)                                                                  A-384 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.23(3H, s), 2.41 (3H, s),          3.49(3H, s), 5.81 (1H, s), 6.27(1H,                                          s), 7.32-7.92(8H, m), 8.67(1H, s)                                            A-388 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.22(3H, s), 2.40(3H, s),           2.42(3H, s), 3.48(3H, s), 5.79(1H,                                           s), 6.31(1H, s), 7.18-7.83(7H, m), 7.87(1H, dd, J=7.3, 1.8), 8.67(1H,          s)                                                                          A-391 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.22(3H, s), 2.42(3H, s),           3.48(3H, s), 3.86(3H, s), 5.79(1H,                                           s), 6.32(1H, s), 6.91-6.97(2H, m), 7.41-7.53(2H, m), 7.70(1H, dd,              J=7.3, 1.2), 7.85-                                                           7.92(3H, m), 8.68(1H, s)                                                     A-392 mp 60.0˜64.0° C.                                           A-396 mp 104.0˜106.0° C.                                       __________________________________________________________________________

                                      TABLE 39                                    __________________________________________________________________________    No Physical data                                                              __________________________________________________________________________    A-503                                                                             .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.23(3H, s), 2.38(3H, s),               3.48(3H, s), 5.82(1H, s),                                                    6.24(1H, s), 7.29-7.60(5H, m), 7.69(1H, dd, J=7.3, 1.8), 7.88(1H, dd,          J=7.3, 1.2),                                                                 8.63(1H, s)                                                                  A-512 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.23(3H, s), 2.40(3H, s),           3.48(3H, s), 5.83(1H, s),                                                    6.26(1H, s), 7.29-7.55(6H, m), 7.69(1H, dd, J=7.3, 1.8), 7.89(1H, dd,          J=7.3, 1.8),                                                                 8.65(1H, s)                                                                  A-504 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.23(3H, s), 2.42(3H, s),           3.49(3H, s), 5.80(1H, s),                                                    6.27(1H, s), 7.27-7.82(7H, m), 7.89(1H, dd, J=7.3, 1.8), 8.66(1H, s)            A-505 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.22(3H, s), 2.42(3H,            s), 3.48(3H, s), 5.80(1H, s),                                                6.27(1H, s), 7.25-7.28(2H, m), 7.42-7.55(2H, m), 7.70(1H, dd, J=7.3,           1.2), 7.87-                                                                  7.96(3H, m), 8.67(1H, s)                                                     A-509 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.21(3H, s), 2.38(3H, s),           3.47(3H, s), 5.70(1H, s),                                                    6.31(1H, s), 6.52(1H, dd, J=3.1, 1.8), 6.93(1H, d, J=3.7), 7.41-7.54(2H        , m),                                                                        7.57(1H, d, J=12), 7.71(1H, dd, J=7.3, 1.2), 7.85(1H, dd, J=7.3),              8.77(1H, s)                                                                 A-508 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.23(3H, s), 2.40(3H, s),           3.49(3H, s), 5.80(1H, s),                                                    6.24(1H, s), 7.44-7.56(2H, m), 7.69-7.75(3H, m), 7.90(1H, dd, J=7.9,           1.8),                                                                        8.65(1 H, s), 8.69-8.74(2H, m)                                               A-510 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.21(3H, s), 2.46(3H, s),           3.48(3H, s), 5.76(1H, s),                                                    6.34(1H, s), 7.08(1H, dd, J=4.9, 3.7), 7.41-7.53(4H, m), 7.71(1H, dd,          J=7.9; 1.8),                                                                 7.83(1H, dd, J=7.9, 1.8), 8.68(1H, s)                                        A-507 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.23(3H, s), 2.45(3H, s),           3.49(3H, s), 5.81(1H, s),                                                    6.26(1H, s), 7.33-7.55(3H, m), 7.70(1H, dd, J=7.3, 1.2), 7.89(1H, dd,          J=7.3, 1.8),                                                                 8.19-8.23(1H, m), 8.65-8.68(2H, m), 9.09(1H, d, J=1.8)                       A-506 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.23(3H, s), 2.51(3H, s),           3.49(3H, s), 5.83(1H, s),                                                    6.26(1H, s), 7.30-7.78(5H, m), 7.92(1H, dd, J=7.3, 1.8), 8.18(1H, d,           J=7.9),                                                                      8.63(1H, s), 8.67(1H, d, J=1.8)                                              A-386 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.22(3H, s), 2.40(3H, s),           3.48(3H, s), 5.79(3H, s),                                                    6.28(1H, s), 7.43-7.90(8H, m), 8.66(1H, s)                                   E-385 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.36(3H, s), 2.44(3H, s),           3.44(3H, s), 5.89(1H, s),                                                    6.10(1H, s), 7.35-7.89(7H, m), 8.01(1H, dd, J=7.3, 1.2), 8.76(1H, s)            E-392 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.36(3H, s), 2.48(3H,            s), 3.45(3H, s), 5.91(1H, s),                                                6.10(1H, s), 7.40-7.70(5H, m), 8.02(1H, dd, J=7.3, 1.2), 8.09(1H, d,           J=7.9),                                                                      8.18(1H, s), 8.77(1H, s)                                                     E-396 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.36(3H, s), 2.43(3H, s),           3.44(3H, s), 5.90(1H, s),                                                    6.08(1H, s), 7.39-8.03(7H, m), 8.76(1H, s)                                 __________________________________________________________________________

                                      TABLE 40                                    __________________________________________________________________________    No  Physical data                                                             __________________________________________________________________________    E-503                                                                             .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.36(3H, s), 2.40(3H, s),               3.43(3H, s), 5.91(1H, s),                                                    6.07(1H, s), 7.19-7.52(5H, m), 7.65(1H, dd, J=7.3, 1.2), 8.00(1H, dd,          J=7.9, 1.8),                                                                 8.71(1H, s)                                                                  E-365 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.56(1.57)(3H, d, J=6.7),           2.32(2.35)(3H, s), 3.33(3.38)                                                (3H, s), 5.29(5.31)(1H, q, J=6.7), 5.71(5.80)(1H, s), 5.74(5.78)(1H,           s), 7.29-                                                                    7.63(8H, m), 8.47(8.49)(1H, s)                                               E-373 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.57(1.59)(3H, d, J=6.7),           2.31(2.35)(3H, s), 3.32(3.38)                                                (3H, s), 5.38(5.39)(1H, q, J=6.7), 5.72(5.76)(1H, s), 5.72(5.79)(1H,           s), 7.28-                                                                    7.63(8H, m), 8.51 (8.53)(1H, s)                                              E-361 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.59(1.60)(3H, d, J=6.7),           2.32(2.35)(3H, s), 3.31(3.37)                                                (3H, s), 5.33(1H, q, J=6.7), 5.73(5.80)(1H, s), 5.76(5.79)(1H, s),             7.23-7.65(9H,                                                                m), 8.47(8.51(1H, s)                                                         E-372 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.59(1.60)(3H, d, J=6.7),           2.32(2.35)(3H, s), 3.32(3.38                                                 )(3H, s), 5.38(1H, q, J=6.7), 5.73(5.76)(1H, s), 5.75(5.81)(1H, s),            7.29-7.64(8H,                                                                m), 8.50(8.53)(1H, s)                                                        E-504 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.36(3H, s), 2.45(3H, s),           3.44(3H, s), 5.90(1H, s),                                                    6.10(1H, s), 7.26-8.03(8H, m), 8.75(1H, s)                                   E-505 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.36(3H, s), 2.46(3H, s),           3.44(3H, s), 5.90(1H, s),                                                    6.10(1H, s),7.25-7.69(5H, m), 7.93-8.04(3H, m), 8.77(1H, s)                  E-384 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.36(3H, s), 2.44(3H, s),           3.44(3H, s), 5.90(1H, s),                                                    6.10(1H, s), 7.32-8.07(8H, m), 8.76(1H, s)                                   E-388 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.35(3H, s), 2.40(3H, s),           2.45(3H, s), 3.44(3H, s), 5.90                                               (1H, s), 6.14(1H, s), 7.22-7.83(7H, m), 8.01(1H, dd, J=7.3, 1.2),              8.76(1H, s)                                                                 E-382 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.36(3H, s), 2.45(3H, s),           3.44(3H, s), 5.89(1H, s), 6.11                                               (1H, s), 7.07-7.14(2H, m), 7.38-7.51(2H, m), 7.67(1H, dd, J=7.9, 1.2),         7.88-                                                                        8.03(3H, m), 8.77(1H, s)                                                     E-393 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.36(3H, s), 2.47(3H, s),           3.44(3H, s), 5.90(1H, s), 6.09                                               (1H, s), 7.39-7.53(2H, m), 7.66-7.69(3H, m), 8.01-8.04(3H, m),                 8.76(1H, s)                                                                 E-507 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 2.36(3H, s), 2.48(3H, s),           3.44(3H, s), 5.90(1H, s),                                                    6.10(1H, s), 7.34-8.67(7H, m), 8.77(1H, s), 9.09(1H, d, J=1.8)                  E-508 mp 143˜144° C.                                        __________________________________________________________________________

                                      TABLE 41                                    __________________________________________________________________________    No  Physical data                                                             __________________________________________________________________________    N-87                                                                              .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.45-1.74(4H, m), 2.04-2.36(2H,         m), 2.13(3H, s), 2.65-                                                       2.70(2H, m), 3.42(3H, s), 5.22(1H, d, J=12.2), 5.28(1H, d, J=12.2),            5.81(1H, s),                                                                 7.30-7.61(8H, m)                                                             N-36 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.53-1.75(4H, m), 2.13-2.37(2        H, m), 2.16(3H, s), 2.32(3H,                                                 s), 2.69(2H, t, J=6.1), 3.43(3H, s), 4.99(1H, d, J=12.2), 5.08(1H, d,          J=1.2.2),                                                                    5.73(1H, s), 6.68-6.71(2H, m), 7.02(4H, d, J=7.9), 7.33-7.61(4H, m)             N-55 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.55-1.75(4H, m),                 2.08(3H, sy, 2.12-2.37(2H, m), 2.23                                          (3H, s), 2.28(3H, s), 2.68(2H, t, J=6.1), 3.42(3H, s), 4.96(1H, d,             J=12.2), 5.06(1H,                                                            d, J=12.2), 5.73(1H, s), 6.75(1H, s), 6.63(1H, s), 7.33-7.65(4H, m)             N-84 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.52-1.73(4H, m),                 2.08-2.35(2H, m), 2.14(3H, s), 2.68(2H,                                      td, J=6.1, 2.4), 3.42(3H, s), 5.21(1H, d, J=12.2), 5.28(1H, d,                 J=12.2), 5.82(1H, s),                                                        6.99-7.08(2H, m), 7.31-7.64(6H, m)                                           N-103 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.51-1.73(4H, m), 2.07-2.18(        1H, m), 2.18(3H, s), 2.26-                                                   2.37(1H, m), 2.65-2.71(2H, m), 3.43(3H, s), 5.25(1H, d, J=12.2),               5.31(1H, d,                                                                  J=12.8), 5.82(1H, s), 7.32-7.75(8H, m)                                       N-110 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.52-1.74(4H, m), 2.07-2.37(        2H, m), 2.12(3H, s), 2.68(2H,                                                td, J=6.1, 1.8), 3.43(3H, s), 5.22(1H, d, J=12.8), 5.29(1H, d,                 J=12.2), 5.80(1H, s),                                                        7.32-7.72(7H, m)                                                             N-324 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.18(6H, d, J=6.7),                 1.56-1.73(4H, m), 1.85(3H, s), 2.04-                                         2.16(1H, m), 2.23-2.35(2H, m), 2.69(2H, t, J=6.7), 3.42(3H, s),                3.42-3.68(4H, m),                                                            4.90(1H, d, J=11.6), 4.97(1H, d, J=12.2), 5.80(1H, s),7.30-7.59(4H, m)       O-87 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.57-1.83(4H, m), 2.1-2.20(4H        , m), 2.32-2.42(1H, m),                                                      2.61-2.65(2H, m), 3.42(3H, s), 5.21(1H, d, J=12.8), 5.43(1H, d,                J=12.8), 5.83(1H,                                                            s), 7.23-7.66(8H, m)                                                         O-103 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.63-1.83(4H, m), 2.10-2.22(        4H, m), 2.33-2.41 (1H, m),                                                   2.61-2.66(2H, m), 3.42(3H, s), 5.24(1H, d, J=12.8), 5.47(1H, d,                J=12.8), 5.83(1H,                                                            s), 7.29-7.46(3H, m), 7.58-7.63(3H, m), 7.74(2H, d, J=8.55)                  O-324 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.18(6H, d, J=6.1),                 1.65-1.81(4H, m), 1.91(3H, s), 2.18-                                         2.35(4H, m), 2.60-2.63(2H, m), 3.41 (3H, s), 3.41-3.48(2H, m),                 3.59-3.66(2H, m),                                                            4.90(1H, d, J=12.2), 5.12(1H, d, J=12.2), 5.81(1H, s), 7.29-7.42(3H,           m), 7.55-                                                                    7.58(1H, m)                                                                  O-66 mp 91.0˜92.0° C.                                            O-69 .sup.1 H-NMR(CDCl.sub.3) δ ppm: 1.61-1.84(4H, m), 2.08-2.19(1        H, m), 2.34-2.44(1H, m),                                                     2.60-2.65(2H, m), 3.45(3H, s), 5.53(1H, d, J=12.8), 5.63(1H, d,                J=12.8), 5.87(1H,                                                            s), 7.30-7.66(4H, m), 7.84(1H, d, J=1.8), 8.33(1H, t, J=1.2)               __________________________________________________________________________

The following Test Examples illustrate the effects of the fungicide andinsecticide of this invention.

I. Controlling effects on various plant diseases by foliage application(pot experiment)

Experimental Method

A test compound was dissolved in a small amount ofN,N-dimethylformamide, and the solution was diluted to a givenconcentration with distilled water containing a spreader. Thus, a liquidsample to be tested was prepared. The liquid sample was sprayed to testplants, and 24 hours thereafter, pathogens were inoculated by the methoddescribed below.

The percent control was calculated according to the following equation:##EQU1##

Test Example 1

Controlling effect on Pyricularia oryzae

Two-week rice seedlings (cv.: AICHIASAHI) were transplanted in plasticcups (each 9 cm in diameter) and cultivated further 2 weeks. The testcompound in the form of a solution or a suspension was sprayed to thefoliage of the rice seedlings, to which a conidia suspension ofPyricularia oryzae cultured in an oatmeal medium was inoculated byspraying. After the inoculation, the test plant was kept in a moistchamber (28° C., 100% R.H.) for 24 hours, followed by cultivation in agreenhouse for 5 days. Six days after the inoculation, the number oflesions on the leaves of the inoculated plant was measured to calculatethe percent control.

The results are as follows.

                  TABLE 42                                                        ______________________________________                                                     Controlling effect on Pvricularia                                   orvzae by foliage application at 500                                         Compound No. ppm (percent control)                                          ______________________________________                                        A-67         90                                                                 A-68 90                                                                       A-69 100                                                                      A-87 90                                                                       A-102 97                                                                      A-103 100                                                                     A-110 90                                                                      A-147 97                                                                      A-323 100                                                                     A-327 97                                                                      A-373 97                                                                      A-385 97                                                                      A-393 97                                                                      E-100 90                                                                      I-41 90                                                                       Reference: Fthalide 97                                                      ______________________________________                                    

Test Example 2

Controlling effect on Sphaerotheca fuliginea

Seeds of cucumber (cv.: TSUKUBASHIROIBO) were sown in plastic cups (each9 cm in diameter), followed by cultivation for 2 to 3 weeks. The liquidtest sample in the form of a solution or suspension was sprayed on thesurface of their first leaves. The pathogen was inoculated to the leavesby spraying a conidia suspension of Sphaerotheca fuliginea which hadbeen cultured on the cucumber leaves. After the inoculation, the plantswere kept in a greenhouse at 20° C. for 10 days. Then, the infected areaon the leaf was observed, and the percent control was calculated.

The results are as follows.

                  TABLE 43                                                        ______________________________________                                                    Controlling effect on Sphaerotheca                                   fuliginea by foliage application at                                          Compound No. 500 ppm (percent control)                                      ______________________________________                                        A-12        100                                                                 A-31 100                                                                      A-36 100                                                                      A-41 100                                                                      A-44 100                                                                      A-55 100                                                                      A-67 100                                                                      A-68 100                                                                      A-69 100                                                                      A-87 100                                                                      A-102 100                                                                     A-103 100                                                                     A-110 100                                                                     A-327 100                                                                     A-323 100                                                                   ______________________________________                                    

                  TABLE 44                                                        ______________________________________                                                      Controlling effect on Sphaerotheca                                 fuliginea by foliage application at                                          Compound No. 500 ppm (percent control)                                      ______________________________________                                        A-373         100                                                               A-385 100                                                                     A-393 100                                                                     D-36 100                                                                      D-41 100                                                                      D-103 100                                                                     E-12 100                                                                      E-36 100                                                                      E-103 100                                                                     E-323 100                                                                     F-103 100                                                                     I-12 100                                                                      I-41 100                                                                      Reference: Fenarimol 100                                                    ______________________________________                                    

Test Example 3

Controlling effect on Botrytis cinerea

The seeds of cucumber (cv.: TSUKUBASHIROIBO) were sown in plastic cups(each 9 cm in diameter), followed by cultivation for 2 to 3 weeks. Thetest compound in the form of a solution or suspension was sprayed to thesurface of their first leaves, and mycelial disks (4 mm φ) of Botrvtiscinerea cultured on the potato sucrose agar medium were put on the leafsurfaces to inoculate the cucumber seedlings with the pathogen. Theplants were kept in a moist chamber at 20° C. for 3 days. The diameterof the lesions on the leaves was measured and the percent control wascalculated.

The results are as follows.

                  TABLE 45                                                        ______________________________________                                                      Controlling effect on Botrvtis cinerea                             by foliage application at 500 ppm                                            Compound No (percent control)                                               ______________________________________                                        A-36          70                                                                A-67 70                                                                       A-87 70                                                                       A-102 70                                                                      A-110 70                                                                      A-323 70                                                                      A-327 70                                                                      E-323 70                                                                      I-41 70                                                                       Reference: iprodione 100                                                    ______________________________________                                    

Test Example 4

Controlling effect on Pseudoperonospora cubensis

The seeds of cucumber (var.: TSUKUBASHIROIBO) were sown in plastic cups(each 9 cm in diameter), followed by cultivation for 2 to 3 weeks. Thetest compound in the form of a solution or suspension was sprayed to thesurface of their first leaves, and a zoosporangia suspension ofPseudoperonospora cubensis cultured on cucumber leaves was dropped onthe above leaf surfaces to inoculate the test plants with the pathogen.After the inoculation, the plants were kept in a moist chamber at 20° C.for 10 days. Then, the area of the lesions around the inoculum wereobserved and the percent control was calculated.

The results are as follows.

                  TABLE 46                                                        ______________________________________                                                      Controlling effect on                                              Pseudoperonospora cubensis by                                                 foliage application at 500 ppm                                               Compound No. (percent control)                                              ______________________________________                                        A-65          100                                                               A-69 100                                                                      A-385 100                                                                     A-393 100                                                                     Reference: benalaxyl  99                                                    ______________________________________                                    

Test Example 5

Controlling effect on Erysiphe graminis f. sp. tritici

The seeds of wheat (cv.: NORIN No. 61) were sown in plastic cups (each 9cm in diameter), followed by cultivation for 2 to 3 weeks. The testcompound in the form of a solution or suspension was sprayed to theseedlings, and conidia of Erysiphe graminis f sp. tritici cultured onwheat leaves were dropped on the test plants to inoculate the plantswith the pathogen. After the inoculation, the plants were kept in agreenhouse at 20° C. for 10 days. The infected area on the leaf wasobserved, and the percent control was calculated.

The results are as follows.

                  TABLE 47                                                        ______________________________________                                                       Controlling effect on Erysiphe                                    graminis f. sp. tritici by foliage                                            application at 500 ppm                                                       Compound No. (percent control)                                              ______________________________________                                        A-12           97                                                               A-22 90                                                                       A-36 97                                                                       A-67 90                                                                       A-68 90                                                                       A-69 90                                                                       A-76 97                                                                       A-102 97                                                                      A-103 97                                                                      A-323 97                                                                      D-36 97                                                                       D-41 90                                                                       D-65 90                                                                       D-67 90                                                                       D-68 97                                                                       D-69 97                                                                       D-87 90                                                                       D-103 97                                                                      E-36 90                                                                       F-69 100                                                                      I-12 90                                                                       Reference: Fenarimol 97                                                     ______________________________________                                    

II. Insecticidal Activity

Test Example 6

Insecticidal activity against Myzus persicae

A lamina of Chinese cabbage (3 cm in diameter) was put upside down on0.3% agar gel, inoculated with apterous mature insects, and kept at 25°C. for a day to count the number of delivery young insects. Afterremoving the mature insects, test liquid at a given concentration wassprayed to the young insects on the lamina of Chinese cabbage. Thenumber of the insects killed after 48 hours at 25° C. was counted tojudge the effect. The test liquid was adjusted to a given concentrationby dissolving the compound in a small amount of N,N-dimethylformamideand being diluted with distilled water containing a surfactant.

The compounds No. A-385, 392, 393, and 396 gave the killed insectspercentage of 90, 100, 88, and 100% at 250 ppm, respectively.

Effect of Invention

As described above, this invention provides novel α-substituted benzylheterocyclic derivatives having potent fungicidal and insecticidalactivity and low toxicity, intermediates for their production, andfungicides and insecticides containing them as an active ingredient.

What is claimed is:
 1. A compound of the formula (I): ##STR21## whereinR¹ is an optionally substituted imidazoyl is optionally substitutedaryl; R³ is hydrogen, alkyl, alkenyl, or alkynyl; R⁴ is hydrogen, alkyl,alkoxy, halogen, nitro, cyano, or halogenated alkyl; M is (1) oxygen,(2) S(O)_(i) wherein i is 0, 1, or 2, (3) NR⁵ wherein R⁵ is hydrogen,alkyl, or acyl, (4) --Q--N═C(R⁶)-- wherein Q is oxygen or NR⁷ wherein R⁷is hydrogen alkyl, or acyl; R⁶ is hydrogen, alkyl, acyl, alkylthio,alkylsulfinyl, alkylsulfonyl, halogenated alkyl, cyano, alkoxycarbonyl,alkoxyalkyl, optionally substituted amino, or cycloalkyl, or R² and R⁶taken together form a monocyclic group or a fused polycyclic groupoptionally having a hetero atom, (5) --B--C(R⁸)═N-- wherein B is oxygenor sulfur and R⁸ is hydrogen, alkyl, acyl, alkylthio, alkylsulfinyl,alkylsulfonyl, halogenated alkyl, cyano, alkoxycarbonyl, alkoxyalkyl,optionally substituted amino, or cycloalkyl, (6) --CH═N--N═C(R⁹)--wherein R⁹ is hydrogen, alkyl, cyano, cycloalkyl, or halogenated alkyl,or (7) --CH═N--A--(CR¹⁰ R¹¹)m-- wherein R¹⁰ and R¹¹ are independentlyhydrogen, alkyl, cyano, or halogenated alkyl, A is oxygen or NR¹²wherein R¹² is hydrogen, alkyl, or acyl, and m is 0 or 1; and n is 0, 1,or
 2. 2. The compound of claim 1 wherein R¹ is optionally substitutedimidazol-2-yl.
 3. The compound of claim 1 wherein R¹ is1-methylimidazol-2-yl.
 4. The compound of claim 1 wherein R² is phenyloptionally substituted with 1 to 3 substituents selected from the groupconsisting of halogen, lower alkyl, halogenated lower alkyl, loweralkoxy, halogenated lower alkoxy, lower alkylthio, phenyl, and phenoxy.5. The compound of claim 1 wherein R² is phenyl unsubstituted orsubstituted with 1 to 3 substituents selected from the group consistingof lower alkoxy, halogenated lower alkoxy, halogenated lower alkyl,halogen and lower alkyl.
 6. The compound of claim 1 wherein R² isphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-methylphenyl,3-methylphenyl, 4-methylphenyl, 2,5-dimethylphenyl, 3,4-dimethylphenyl,4-chloro-2-methylphenyl, 3,4-dichlorophenyl, 3-trifluoromethylphenyl,4-trifluoromethylphenyl, 4-methoxyphenyl, 3-trifluoromethyloxyphenyl,4-trifluoromethyloxyphenyl.
 7. The compound of claim 1 wherein R³ ismethyl.
 8. The compound of claim 1 wherein R⁴ is hydrogen.
 9. Thecompound of claim 1 wherein M is oxygen, --O--N═C(R⁶)--,--CH═N--N═C(R⁹)--, or --CH═N--O--(CR¹⁰ R¹¹)m-- wherein each symbol is asdefined in claim
 1. 10. The compound of claim 1 wherein M is oxygen,--O--N═C(CH₃)--, --O--N═C(SCH₃)--, --O--N═C(CN)--, --O--N═C(CF₃)--,--CH═N--N═C(CH₃)--, --CH═N--O--CH(CH₃)--, or --CH═N--O--C(CH₃)₂ --. 11.The compound of claim 1 which is;a compound wherein R¹ is1-methylimidazol-2-yl, R² is 2-methylphenyl, R³ is methyl, R⁴ ishydrogen, M is oxygen and n is 1; or a compound wherein R¹ is1-methylimidazol-2-yl, R² is 4-chloro-2-methylphenyl, R³ is methyl, R⁴is hydrogen, M is oxygen and n is
 1. 12. An agrochemical compositionwhich contains the compound of claim 1 as an active ingredient.
 13. Afungicidal composition which contains the compound of claim 1 as anactive ingredient.
 14. An insecticidal composition which contains thecompound of claim 1 as an active ingredient.
 15. The compound of claim 1which is a compound of the formula (IV): ##STR22## wherein each symbolis as defined in claim
 1. 16. A compound of the formula (X): ##STR23##wherein each symbol is as defined in claim
 1. 17. A compound of theformula (XII): ##STR24## wherein Y is halogen and the other symbols areas defined in claim
 1. 18. A method for controlling or preventingphytopathogenic fungi which comprises applying as an active ingredient acompound of claim 1, its salt, or its hydrate to a locus wherephytopathogenic fungi propagated or will propagate.
 19. A method formanufacturing a fungicidal composition which comprises admixing thecompound of claim 1, its salt or its hydrate, and a carrier.